WO2015159957A1 - Transparent sheet material with pressure-sensitive adhesive layer, display device, production processes therefor, and pressure-sensitive adhesive sheet - Google Patents
Transparent sheet material with pressure-sensitive adhesive layer, display device, production processes therefor, and pressure-sensitive adhesive sheet Download PDFInfo
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- WO2015159957A1 WO2015159957A1 PCT/JP2015/061745 JP2015061745W WO2015159957A1 WO 2015159957 A1 WO2015159957 A1 WO 2015159957A1 JP 2015061745 W JP2015061745 W JP 2015061745W WO 2015159957 A1 WO2015159957 A1 WO 2015159957A1
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- adhesive layer
- surface material
- pressure
- transparent
- resin composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Definitions
- the present invention relates to a transparent surface material with an adhesive layer, a display device in which a display panel is protected by the transparent surface material, a manufacturing method thereof, and an adhesive sheet.
- the display panel When manufacturing the display device of (1), the display panel is used in a reduced-pressure atmosphere so that no bubbles (voids) remain at the interface between the display panel and the adhesive sheet and at the interface between the transparent surface material and the adhesive sheet. And a transparent surface material are pasted together via an adhesive sheet, and then a method of returning it to an atmospheric pressure atmosphere is employed.
- the display device of (2) When the display device of (2) is manufactured, the display panel and the transparent surface material with the adhesive layer are placed under a reduced pressure atmosphere so that bubbles (voids) do not remain at the interface between the display panel and the adhesive layer. Then, after bonding so that the adhesive layer is in contact with the display panel, a method of returning it to the atmospheric pressure atmosphere is employed.
- the pressure in the bubbles (that is, the pressure in the reduced pressure state) is reduced by returning the display device in the reduced pressure atmosphere to the atmospheric pressure atmosphere.
- the volume of the bubbles decreases due to the pressure difference between the pressure applied to the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer (ie, atmospheric pressure), and the bubbles disappear.
- a conventional pressure-sensitive adhesive sheet or a transparent surface material with a pressure-sensitive adhesive layer it may take time for the bubbles remaining at the interface to disappear. If it takes time for the bubbles remaining at the interface to disappear, the productivity of the display device is lowered.
- the present invention provides a transparent surface with an adhesive layer in which bubbles remaining at the interface between the object to be bonded and the adhesive layer can quickly disappear when the object to be bonded and the transparent surface material are bonded via the adhesive layer.
- Material A transparent surface material with a pressure-sensitive adhesive layer in which bubbles remaining at the interface between the material to be bonded and the pressure-sensitive adhesive layer can quickly disappear when the material to be bonded and the transparent surface material are bonded via the pressure-sensitive adhesive layer.
- Method for manufacturing display device in which bubbles remain at the interface between the display panel and the adhesive layer; method for manufacturing a display device in which bubbles remain at the interface between the display panel and the adhesive layer are suppressed with high productivity And providing a pressure-sensitive adhesive sheet in which bubbles remaining at the interface between the material to be bonded and the pressure-sensitive adhesive sheet can rapidly disappear when bonded to the material to be bonded.
- the inventors have determined the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer. It has been found that it takes time for bubbles to disappear when there are many.
- the transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition, formed on at least one surface of the transparent surface material, and the adhesive layer
- the concentration of hydroxyl groups therein is 100 ⁇ 10 ⁇ 6 to 600 ⁇ 10 ⁇ 6 mol / g, and the concentration of urethane bonds in the adhesive layer is 0 to 150 ⁇ 10 ⁇ 6 mol / g.
- the total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 ⁇ 10 ⁇ 6 to 750 ⁇ 10 ⁇ 6 mol / g.
- the solubility parameter of the adhesive layer is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
- the curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
- the curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound.
- At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond. It is preferable that the transparent surface material with an adhesive layer of the present invention further has a peelable protective film that covers the surface of the adhesive layer.
- the manufacturing method of the transparent surface material with the adhesion layer of this invention is a method of manufacturing the transparent surface material with the adhesion layer of this invention, Comprising: It has the following process ((alpha)) and the following process ((gamma)).
- ( ⁇ ) A step of supplying the liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
- ( ⁇ ) A step of curing the curable resin composition or the partially cured product to form the adhesive layer. It is preferable that the manufacturing method of the transparent surface material with the adhesion layer of this invention further has the following process ((beta)).
- ( ⁇ ) A step of covering the surface of the curable resin composition or the partially cured product with a protective film.
- the step ( ⁇ ) is preferably the following step ( ⁇ 1), the step ( ⁇ ) is the following step ( ⁇ 1), and the step ( ⁇ ) is preferably the following step ( ⁇ 1).
- ( ⁇ 1) The liquid curable resin composition is supplied in a layer form on the surface of the transparent face material, and the curable resin composition supplied on the surface of the transparent face material is partially cured to be partially cured. Forming a layer.
- ( ⁇ 1) A step of covering the surface of the partially cured product layer with a protective film.
- ( ⁇ 1) A step of further curing the partially cured product layer to form the adhesive layer.
- the step ( ⁇ ) is the following step ( ⁇ 21) and the following step ( ⁇ 22), the step ( ⁇ ) is the following step ( ⁇ 2), and the step ( ⁇ ) is the following step ( ⁇ 21). And the following step ( ⁇ 22) is preferred.
- ( ⁇ 21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
- ( ⁇ 22) A step of supplying the curable resin composition to a region surrounded by the weir.
- the display apparatus of this invention has a display panel and the transparent surface material with the adhesion layer of this invention bonded by the said display panel so that the said adhesion layer may contact
- the display device manufacturing method of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are disposed in a reduced pressure atmosphere, and the adhesive layer is the display panel. Laminate and touch to touch.
- the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet made of a cured product of a curable resin composition, and the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet is 100 ⁇ 10 ⁇ 6 to 600 ⁇ 10 ⁇ 6 mol / g, The concentration of urethane bonds in the pressure-sensitive adhesive sheet is 0 to 150 ⁇ 10 ⁇ 6 mol / g. The total of the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is preferably 100 ⁇ 10 ⁇ 6 to 750 ⁇ 10 ⁇ 6 mol / g.
- the solubility parameter of the cured product of the curable resin composition is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
- the curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
- the curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound.
- At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
- the pressure-sensitive adhesive sheet with a protective film of the present invention has the pressure-sensitive adhesive sheet of the present invention and a peelable protective film that covers at least one surface of the pressure-sensitive adhesive sheet.
- the transparent surface material with an adhesive layer of the present invention when the object to be bonded and the transparent surface material are bonded via the adhesive layer, bubbles remaining at the interface between the object to be bonded and the adhesive layer are rapidly generated. Can disappear.
- the method for producing a transparent surface material with an adhesive layer of the present invention the object to be bonded and the transparent surface material are bonded to each other through the adhesive layer, and remain at the interface between the object to be bonded and the adhesive layer. It is possible to produce a transparent surface material with an adhesive layer in which bubbles can disappear quickly. In the display device of the present invention, bubbles remain at the interface between the display panel and the adhesive layer.
- the method for manufacturing a display device of the present invention it is possible to manufacture a display device in which bubbles are prevented from remaining at the interface between the display panel and the adhesive layer with high productivity.
- the pressure-sensitive adhesive sheet of the present invention when the pressure-sensitive adhesive sheet is bonded to the object to be bonded, bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive sheet can quickly disappear.
- FIG. 1 It is sectional drawing which shows an example of the display apparatus of this invention. It is a perspective view which shows the mode of the bubble in the interface of a display panel and an adhesion layer at the time of bonding a transparent surface material and a display panel through the adhesion layer.
- 4 is a graph showing the relationship between the concentration of hydroxyl groups in the adhesive layer and the bubble disappearance time in Examples 1 to 3.
- 6 is a graph showing the relationship between the total concentration of hydroxyl groups and urethane bonds in the adhesive layer in Examples 1 to 3 and the bubble disappearance time.
- 7 is a graph showing the relationship between the concentration of hydroxyl groups in the adhesive layer and the bubble disappearance time in Examples 4 to 6.
- 7 is a graph showing the relationship between the total concentration of hydroxyl groups and urethane bonds in the adhesive layer in Examples 4 to 6 and the bubble disappearance time.
- Transparent in the transparent surface material means that after the surface material and the display surface of the display panel are bonded to each other through the adhesive layer without bubbles and / or voids, the whole or a part of the display image on the display panel is optical. It means a state that can be visually recognized through the face material without receiving any significant distortion. Therefore, even if part of the light incident on the face material from the display panel is absorbed and reflected by the face material, or the visible material has a low visible ray transmittance due to a change in optical phase, the surface If the display image on the display panel can be viewed through the material without optical distortion, it can be said to be “transparent”.
- the “liquid curable resin composition” means that the curable resin composition is in a liquid state without containing a solvent.
- the “cured product of the curable resin composition” is a product obtained by curing the curable resin composition until the storage shear modulus at 35 ° C. becomes the target storage shear modulus at 35 ° C. means.
- Partially cured product means that the curable resin composition is cured until the storage shear modulus at 35 ° C. becomes 1/200 to 1/5 of the storage shear modulus at 35 ° C. of the target adhesive layer. Means something.
- Olemer is a compound having a molecular chain composed of repeating structural units (oxyalkylene units, diene units, etc.) and means having a number average molecular weight of 1,000 to 100,000.
- the “low molecular weight polymerizable compound” means a compound having an addition polymerizable unsaturated double bond and a molecular weight of 600 or less.
- (Meth) acrylate means acrylate or methacrylate.
- “Viscosity” is a value measured using an E-type viscometer at 25 ° C.
- “Number average molecular weight of curable oligomer (A)” is a number average molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter referred to as GPC). In addition, in GPC, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated
- “Number average molecular weight of non-curable oligomer (C1)” is a hydroxyl value A (KOH mg / g) measured in accordance with JIS K 1557-1: 2007 and within one molecule of non-curable oligomer (C).
- SP value Adhesion layer solubility parameter of a cured product of the curable resin composition calculated using the Fedors formula.
- “Storage shear modulus of adhesive layer (or weir) at 35 ° C.” is measured using a rheometer (Modular Rheometer Physica MCR-301, manufactured by Anton Paar), and a measuring spindle and a transparent plate.
- the gap is the same as the thickness of the adhesive layer (or weir)
- an uncured curable resin composition is placed in the gap, and heat and light necessary for curing are added to the uncured curable resin composition
- the storage shear modulus of the curing process is measured at a measurement frequency of 1 Hz, and the measured value in the curing condition when forming the adhesive layer (or weir) is defined as the storage shear modulus of the adhesive layer (or weir).
- the transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition for forming an adhesive layer formed on the surface of the transparent surface material.
- the adhesive layer may be formed on at least one surface of the transparent surface material, or may be formed on both surfaces of the transparent surface material.
- the transparent surface material with an adhesive layer of the present invention may further have a frame-like weir surrounding the adhesive layer in contact with the periphery of the adhesive layer, if necessary.
- the transparent surface material with an adhesive layer of the present invention may further have a peelable protective film that covers the surface of the adhesive layer, if necessary.
- Transparent surface material As a form of the transparent surface material, a protective plate provided on the image display surface side (viewing side) of the display panel to protect the display panel; a coordinate provided on the contacted side (viewing side) of a coordinate input device such as a touch panel A protective plate for protecting the input device; for example, a substrate with a transparent electrode constituting a touch panel portion in a display device with a touch panel.
- a glass plate or a transparent resin plate can be mentioned.
- the glass plate is not only highly transparent with respect to light emitted from and reflected from the display panel, but also has light resistance, low birefringence, high planar accuracy, surface scratch resistance, and high mechanical strength. Is most preferred.
- a glass plate is also preferred from the viewpoint of sufficiently transmitting light for curing the photocurable resin composition in the production process described later.
- a glass material such as soda lime glass can be mentioned, and a high transmission glass (also referred to as white plate glass) having a lower iron content and less bluishness is more preferable. Tempered glass may be used to increase safety. In particular, when a thin glass plate is used, it is preferable to use a chemically strengthened glass plate.
- the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the transparent face material may be subjected to a surface treatment in order to improve adhesion with the adhesive layer.
- a surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent, a method of forming a silicon oxide thin film by an oxidation flame using a frame burner, and the like.
- the pressure-sensitive adhesive layer is a layer made of a transparent resin obtained by curing a liquid pressure-sensitive adhesive layer-forming curable resin composition.
- the concentration of the hydroxyl group in the adhesive layer is 100 ⁇ 10 ⁇ 6 to 600 ⁇ 10 ⁇ 6 mol / g, preferably 250 ⁇ 10 ⁇ 6 to 550 ⁇ 10 ⁇ 6 mol / g, and 300 ⁇ 10 ⁇ 6 to 500 ⁇ 10 ⁇ 6 mol / g is more preferable. If the concentration of the hydroxyl group in the adhesive layer is 100 ⁇ 10 ⁇ 6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material, and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) It becomes good.
- the bonding between the transparent surface material with the adhesive layer and the object to be bonded fails.
- the transparent surface material with the adhesive layer is peeled off from the material to be bonded, the pressure-sensitive adhesive layer is difficult to cohesively break down, and a part of the pressure-sensitive adhesive layer hardly remains in the material to be bonded.
- the object to be bonded cannot be reused.
- the concentration of the hydroxyl group in the adhesive layer is 600 ⁇ 10 ⁇ 6 mol / g or less, when the transparent surface material with the adhesive layer and the object to be bonded are bonded, the interface between the object to be bonded and the adhesive layer is obtained. The remaining bubbles can disappear quickly.
- the concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. Calculated from the mixing ratio of raw materials.
- concentration of the hydroxyl group of a curable oligomer (A) and a non-curable oligomer (C) is calculated
- the hydroxyl group concentration of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
- the concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. It can adjust within the said range by adjusting the compounding ratio of a raw material.
- the concentration of urethane bonds in the adhesive layer is 0 to 150 ⁇ 10 ⁇ 6 mol / g, preferably 30 ⁇ 10 ⁇ 6 to 95 ⁇ 10 ⁇ 6 mol / g, and 50 ⁇ 10 ⁇ 6 to 90 ⁇ 10 ⁇ . 6 mol / g is more preferable.
- the concentration of the urethane bond in the adhesive layer is 30 ⁇ 10 ⁇ 6 mol / g or more, the adhesive layer is less likely to cohesively break down when the transparent surface material with the adhesive layer is peeled off from the object to be bonded. Part of the layer hardly remains on the object to be bonded.
- the pressure-sensitive adhesive layer preferably has no urethane bond from the viewpoint of the disappearance of bubbles, but preferably has a urethane bond when it is desired to increase the curing rate of the curable oligomer (A).
- the concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it calculates
- the concentration of the urethane bond in the curable oligomer (A) and the non-curable oligomer (C) is determined by calculation from the molar ratio of raw materials when the oligomer is synthesized.
- the concentration of the urethane bond of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
- the concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it can adjust within the said range by adjusting the compounding ratio of each raw material. Especially, when it is a combination of the curable oligomer (A1), the low molecular weight polymerizable compound (B1) and the non-curable oligomer (C1), the concentration of the urethane bond contained in the curable oligomer (A1) and each raw material By adjusting both of the blending ratios, it can be adjusted within the above range.
- the total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 ⁇ 10 ⁇ 6 to 750 ⁇ 10 ⁇ 6 mol / g, and 250 ⁇ 10 ⁇ 6 to 600 ⁇ 10 ⁇ 6 mol. / G is more preferable.
- the curing rate of the curable oligomer (A) is high, and the adhesive layer and the transparent layer are transparent. Adhesion with the face material and adhesion between the adhesive layer and the object to be bonded (display panel or the like) are improved.
- the transparent surface material with the adhesive layer is peeled from the object to be bonded.
- the adhesive layer is difficult to cohesively break, and a part of the adhesive layer hardly remains on the object to be bonded.
- the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 600 ⁇ 10 ⁇ 6 mol / g or less, the transparent surface material with the adhesive layer and the object to be bonded are bonded. In addition, bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more rapidly.
- the solubility parameter of the adhesive layer is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 , and 18.0 to 18.45 (J / Cm 3 ) 1/2 is more preferable.
- the solubility parameter is 17.5 (J / cm 3 ) 1/2 or more, the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) are good. It becomes. If the solubility parameter is 18.5 (J / cm 3 ) 1/2 or less, it remains at the interface between the object to be bonded and the adhesive layer when it is bonded to the transparent surface material with the adhesive layer and the object to be bonded. Bubbles can disappear more quickly.
- the storage shear modulus of the adhesive layer at 35 ° C. is preferably 1 ⁇ 10 3 to 300 ⁇ 10 3 Pa, more preferably 1 ⁇ 10 3 to 100 ⁇ 10 3 Pa, and more preferably 1 ⁇ 10 3 to 50 ⁇ 10 3 Pa. Further preferred. If the storage shear modulus is 1 ⁇ 10 3 Pa or more, the shape of the adhesive layer can be maintained. Moreover, even when the thickness of the adhesive layer is relatively large, the thickness can be kept uniform throughout the adhesive layer, and when the transparent surface material with the adhesive layer and the display panel are bonded, Air bubbles are unlikely to occur at the interface with the layer. When the storage shear modulus is 300 ⁇ 10 3 Pa or less, the adhesive layer can exhibit good adhesion when bonded to a display panel.
- the molecular mobility of the cured product of the first composition constituting the adhesive layer is relatively high, after bonding the display panel and the transparent surface material with the adhesive layer under a reduced pressure atmosphere, the atmospheric pressure atmosphere
- the difference between the pressure inside the bubble (that is, the pressure of the reduced pressure atmosphere in the reduced pressure state) and the pressure applied to the adhesive layer (that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere) The volume of the bubbles is easily reduced by the pressure, and the gas in the bubbles with the reduced volume is easily dissolved and absorbed in the adhesive layer.
- the thickness of the adhesive layer is preferably 0.03 to 2 mm, more preferably 0.1 to 0.8 mm. If the thickness of the pressure-sensitive adhesive layer is 0.03 mm or more, the pressure-sensitive adhesive layer effectively buffers an impact or the like due to an external force from the transparent surface material side, and the display panel or the like can be protected. Further, in the manufacturing method of the display device, even if foreign matter not exceeding the thickness of the adhesive layer is mixed between the display panel and the transparent surface material with the adhesive layer, the thickness of the adhesive layer is not significantly changed. Little impact on transmission performance. If the thickness of the adhesive layer is 2 mm or less, bubbles hardly remain in the adhesive layer, and the entire thickness of the display device does not become unnecessarily thick.
- a method for adjusting the thickness of the adhesive layer there are a method for adjusting the supply amount of the liquid curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material, a method for adjusting the thickness of the weir, etc. Can be mentioned.
- the adhesive layer forming curable resin composition is not particularly limited as long as it can form an adhesive layer.
- the curable resin composition for forming an adhesive layer from the viewpoint of the adhesiveness between the adhesive layer and the transparent surface material and the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer.
- the 1st composition mentioned later is mentioned preferably.
- the first composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition as necessary. And a non-curable oligomer (C) having no polymerizable unsaturated double bond.
- a curable oligomer (A) having an addition polymerizable unsaturated double bond a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition as necessary.
- a non-curable oligomer (C) having no polymerizable unsaturated double bond.
- the non-curable oligomer (C) is not included, either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) have a hydroxyl group.
- At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
- the first composition may be a photocurable resin composition or a thermosetting resin composition.
- the first composition is preferably a photocurable resin composition further blended with a photopolymerization initiator (D) because it can be cured at a low temperature and has a high curing rate.
- D photopolymerization initiator
- the first composition is a photocurable resin composition, a high temperature is not required for curing, so that there is little risk of damage to the display panel or the like due to high temperatures.
- the first composition may contain an additive as necessary.
- the addition polymerizable unsaturated double bond of the curable oligomer (A) is preferably an acryloyloxy group or a methacryloyloxy group, particularly preferably an acryloyloxy group, from the viewpoint of curability of the first composition.
- the viscosity of the curable oligomer (A) is preferably 1 to 800 Pa ⁇ s, more preferably 2 to 600 Pa ⁇ s. When the viscosity of the curable oligomer (A) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later.
- a curable oligomer (A) may be used individually by 1 type, and may use 2 or more types together.
- the curable oligomer (A) has a number average molecular weight of 1,000 to 100,000 from the viewpoint of the curability of the first composition and the mechanical properties of the adhesive layer, and is an addition polymerizable unsaturated double bond.
- a blended curable oligomer (A1) having an average number of 1.8 to 4 is preferred.
- the curable oligomer (A) has a number average molecular weight of 1,000 to 1,000 from the viewpoint that bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more quickly and display unevenness of the display device is suppressed. It is preferably 20,000 and blended with a curable oligomer (A2) having an average number of addition polymerizable unsaturated double bonds of 0.5 to 1.
- a curable oligomer (A) what mixed the curable oligomer (A1) and the curable oligomer (A2) is more preferable.
- Curable oligomer (A1) The number average molecular weight of the curable oligomer (A1) is 1,000 to 100,000, and preferably 10,000 to 80,000. When the number average molecular weight of the curable oligomer (A1) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later, and it is easy to form an adhesive layer in which display unevenness is suppressed.
- the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 in terms of the curability of the first composition and the mechanical properties of the adhesive layer. 3 is preferred.
- the number of addition polymerizable unsaturated double bonds in one molecule is preferably 2 to 4, but when the curable oligomer (A1) is produced, By-products with less than 2 addition polymerizable unsaturated double bonds may be formed. Therefore, the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 as including by-products.
- curable oligomer (A1) those having a polyoxyalkylene chain or a polydiene chain are preferred, and those having a polyoxyalkylene chain are more preferred from the viewpoint of flexibility and heat-and-moisture resistance.
- curable oligomer (A1) having a polydiene chain an esterified product of maleic anhydride adduct of polyisoprene polymer and 2-hydroxyethyl methacrylate (Kuraray Co., Ltd., UC102 (number average molecular weight: 17,000, addition polymerization) Average number of polymerizable unsaturated double bonds: 2), UC203 (number average molecular weight: 35,000, average number of addition polymerizable unsaturated double bonds: 3), UC-1 (number average molecular weight: about 25,000) )), (Meth) acrylate oligomers of polybutadiene skeleton and the like.
- a curable oligomer (A1) may be used individually by 1 type, and may use 2 or more types together.
- curable oligomer (A1) the following curable oligomer (A11) or curable oligomer (A12) is particularly preferable from the viewpoint of flexibility.
- the curable oligomer (A12) will be described later.
- Monomer (a1) A monomer having a molecular weight of 125 to 600, having one or more acryloyloxy groups and one group that reacts with an isocyanate group.
- Examples of the monomer (a1) include monomers having an active hydrogen-containing group (hydroxyl group, amino group, etc.) and an acryloyloxy group.
- Specific examples of the monomer (a1) include hydroxyalkyl acrylates having a C 2-6 hydroxyalkyl group (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, etc.) Etc.
- the monomer (a1) is preferably a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms.
- a monomer (a1) may be used individually by 1 type, and may use 2 or more types together.
- polystyrene resin examples include polyoxyalkylene polyols (polyoxyethylene glycol, polyoxypropylene polyol, etc.), polyester polyols, polycarbonate polyols, and the like.
- the polyol is preferably a polyoxyalkylene polyol, more preferably a polyoxypropylene polyol, from the viewpoint of flexibility.
- the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 1st composition.
- the polyoxyalkylene polyol which has a polyoxyalkylene chain which consists only of an oxyethylene group and an oxypropylene group is especially preferable from the point that a highly flexible hardened
- the number average molecular weight of the polyol is preferably 4,000 or more, and more preferably 8,000 or more, from the viewpoint of lowering the concentration of urethane bonds in the first composition.
- the number average molecular weight of the polyol is preferably 45,000 or less, more preferably 35,000 or less, from the viewpoint that the viscosity of the first composition is easily within the range described below.
- a polyol may be used individually by 1 type and may use 2 or more types together.
- the polyisocyanate is preferably at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and non-yellowing aromatic diisocyanates.
- aliphatic polyisocyanate examples include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.
- Examples of the alicyclic polyisocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
- Examples of the non-yellowing aromatic diisocyanate include xylylene diisocyanate. Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
- the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is preferably from 1/1 to 1.8 / 1, preferably from 1.05 / 1 or more. 1.5 / 1 or less is more preferable.
- isocyanate group / hydroxyl group is within the above range, it is easy to adjust the viscosity of the first composition to the range described later.
- the monomer (a11) having one addition polymerizable unsaturated double bond and one hydroxyl group in one molecule is reacted so that the ratio of the number of moles of isocyanate group / hydroxyl group is 1/1.
- the curable oligomer (A11) having an average number of addition polymerizable unsaturated double bonds of 2 to 4 A polyol having an average number of hydroxyl groups of 2 and a polyisocyanate having an average number of isocyanate groups of 2 are reacted to obtain a prepolymer having an average number of isocyanate groups of 2, and then hydroxyl groups in one molecule.
- the monomer (a12) having one and having at least one addition polymerizable unsaturated double bond has a ratio of the number of moles of isocyanate group / hydroxyl group of 1/1, and the average number of addition polymerizable unsaturated double bonds is A method of reacting to become 2 to 4.
- the curable oligomer (A12) is the following oligomer.
- a polyol the thing similar to what was used for manufacture of a curable oligomer (A11) can be used.
- the compound having one isocyanate group and one addition polymerizable double bond include a compound represented by CH 2 ⁇ C (R) C (O) O—R 1 —NCO (where R is a hydrogen atom or methyl And R 1 is an alkylene group having 1 to 6 carbon atoms).
- Such compounds include Karenz MOI (registered trademark) (manufactured by Showa Denko KK, R is a methyl group, R 1 has 2 carbon atoms), Karenz AOI (registered trademark) (manufactured by Showa Denko KK, R is a hydrogen atom, And R 1 has 2 carbon atoms.
- Curable oligomer (A2) The number average molecular weight of the curable oligomer (A2) is 1,000 to 20,000, preferably 2,000 to 10,000. When the number average molecular weight of the curable oligomer (A2) is within this range, it is easy to form an adhesive layer that can easily adjust the viscosity of the first composition to a range described later. When the curable oligomer (A) contains the curable oligomer (A2), it is easy to adjust the viscosity of the first composition to a range described later. Since the curable oligomer (A2) has substantially no hydroxyl group, the viscosity of the first composition can be adjusted without adversely affecting the disappearance of bubbles.
- Examples of the addition polymerizable unsaturated double bond of the curable oligomer (A2) include an acryloyloxy group and a methacryloyloxy group.
- the addition polymerizable unsaturated double bond of the curable oligomer (A2) is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of a high curing rate and a highly transparent adhesive layer.
- An acryloyloxy group is particularly preferred because the difference in the reactivity of the addition polymerizable unsaturated double bond between (A2) and the low molecular weight polymerizable compound (B) is reduced, and a homogeneous adhesive layer is formed.
- the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A2) is 0.5 to 1 in terms of the curability of the first composition and the mechanical properties of the adhesive layer, and 0.7 to 1 is preferred.
- the number of addition polymerizable unsaturated double bonds exceeds 1, it becomes an oligomer having crosslinkability, and the storage shear modulus of the cured product of the curable resin composition tends to increase. Therefore, the stress applied to the display panel bonded to the adhesive layer is increased, and display unevenness of the display device is likely to occur. Further, the fluidity of the adhesive layer is lost, and bubbles generated at the interface between the adhesive layer and the display panel during bonding are likely to remain.
- a curable oligomer (A2) may be used individually by 1 type, and may use 2 or more types together.
- curable oligomer (A2) the following curable oligomer (A21) is preferable from the viewpoint of flexibility.
- Examples of the monomer (a1) and polyisocyanate used for the production of the curable oligomer (A21) include the same ones as used for the production of the curable oligomer (A11), and preferred embodiments are also the same.
- Examples of the monool include those similar to those used in the production of the curable oligomer (A11) except for the number of hydroxyl groups, and preferred embodiments are also the same.
- the preferred number of hydroxyl groups in the monool is 0.5 to 1 in one molecule, more preferably 0.7 to 1.
- the molecular weight of the low molecular weight polymerizable compound (B) is 600 or less, preferably 140 to 400. The smaller the molecular weight of the low molecular weight polymerizable compound (B), the better the adhesion between the adhesive layer and the transparent surface material, and the adhesion between the adhesive layer and the object to be bonded (display panel, etc.). If the molecular weight of the low molecular weight polymerizable compound (B) is 140 or more, volatilization of the low molecular weight polymerizable compound (B) when the transparent surface material with adhesive layer and the display device are produced by the method described later can be suppressed.
- the number of addition polymerizable unsaturated double bonds of the low molecular weight polymerizable compound (B) is preferably 1 to 3, more preferably 1 to 2.
- the low molecular weight polymerizable compound (B) is preferably a combination of a compound having one addition polymerizable unsaturated double bond and a compound having two or more addition polymerizable unsaturated double bonds.
- Examples of the addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) include an acryloyloxy group and a methacryloyloxy group.
- the addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of a high curing speed and a highly transparent adhesive layer.
- An acryloyloxy group is particularly preferred because of its high speed.
- a low molecular weight polymeric compound (B) may be used individually by 1 type, and may use 2 or more types together.
- Low molecular weight polymerizable compound (B1) As the low molecular weight polymerizable compound (B), the adhesiveness between the adhesive layer and the transparent surface material, the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.), and the adhesive layer are improved. Incorporating a low molecular weight polymerizable compound (B1) having an addition polymerizable unsaturated double bond and a hydroxyl group bonded to a carbon atom from the viewpoint of easily obtaining a dispersion stabilizing effect of the non-curable oligomer (C1) described later Is preferred.
- the number of hydroxyl groups of the low molecular weight polymerizable compound (B1) is determined by the adhesion between the adhesive layer and the transparent surface material or the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. From the viewpoint, 1 or 2 is preferable, and 1 is particularly preferable.
- Examples of the low molecular weight polymerizable compound (B1) having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
- Examples thereof include acrylate, 6-hydroxyhexyl methacrylate, and phenyl glycidyl ether acrylate.
- Examples of the low molecular weight polymerizable compound (B1) having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.
- hydroxyalkyl methacrylate (2-hydroxypropyl methacrylate) having a hydroxyalkyl group having 3 to 8 carbon atoms from the viewpoint of adhesion between the adhesive layer and the transparent surface material or the object to be bonded.
- 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc.) or phenyl glycidyl ether acrylate is preferred, and phenyl glycidyl ether acrylate is particularly preferred.
- a low molecular weight polymeric compound (B1) may be used individually by 1 type, and may use 2 or more types together.
- Low molecular weight polymerizable compound (B2) The low molecular weight polymerizable compound (B) may further contain a low molecular weight polymerizable compound (B2) having an addition polymerizable unsaturated double bond and no hydroxyl group.
- non-curable oligomer (C) does not react with the curable oligomer (A) and the low molecular weight polymerizable compound (B) when the first composition is cured.
- the non-curable oligomer (C) may or may not have a hydroxyl group.
- a non-curable oligomer (C) may be used individually by 1 type, and may use 2 or more types together.
- the non-curable oligomer (C) When the non-curable oligomer (C) is included in the first composition, the fluidity of the first composition is increased, and the storage shear modulus of the adhesive layer is reduced. Therefore, the non-curable oligomer (C) is obtained by bonding the transparent surface material with the adhesive layer and the object to be bonded in a reduced pressure atmosphere, and then returning the object to the atmospheric pressure atmosphere. This contributes to shortening the time required for the bubbles generated at the interface of the liquid to disappear. In addition, the non-curable oligomer (C) can suppress stress applied to the transparent surface material when the first composition is applied to the surface of the transparent surface material and the first composition is cured.
- the non-curable oligomer (C) can exert the above-mentioned effect in a small amount, but when it has a weir, the diffusion of the non-curable oligomer (C) from the adhesive layer to the weir occurs, so at the interface between the adhesive layer and the weir. There is a possibility that bubbles may be generated or remain when bonded to an object to be bonded due to deformation (for example, a step). Therefore, it is preferable to use the non-curable oligomer (C) within a range of amounts described later.
- Non-curable oligomer (C1) The non-curable oligomer (C) is a non-curable oligomer (from the point that the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) are good. What mix
- blended C1) is preferable.
- the average number of hydroxyl groups in the non-curable oligomer (C1) is preferably 0.8 to 3 in terms of compatibility and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. More preferably, 8 to 2.3.
- the number average molecular weight per hydroxyl group of the non-curable oligomer (C1) is preferably 400 to 8,000, more preferably 600 to 5,000. If the number average molecular weight per hydroxyl group is 400 or more, the polarity of the non-curable oligomer (C1) does not become too high, and the curable oligomer (A), the low molecular weight polymerizable compound (B) and other non-cured compounds. Good compatibility with the functional oligomer (C) is easily obtained.
- a non-curable oligomer (C1) may be used individually by 1 type, and may use 2 or more types together.
- non-curable oligomer (C1) examples include a high molecular weight polyol.
- the non-curable oligomer (C1) is preferably a polyoxyalkylene polyol, a polyester polyol, a polycarbonate polyol, or a polybutadiene polyol from the viewpoint of flexibility and compatibility.
- the curable oligomer (A) is a urethane acrylate using a polyoxyalkylene polyol as a raw material
- the non-curable oligomer (C1) is more preferably a polyoxyalkylene polyol from the viewpoint of better compatibility.
- the polyoxyalkylene polyol include polyoxyalkylene diols such as polyoxyethylene glycol, polyoxypropylene diol, polyoxypropylene triol, and polyoxytetramethylene glycol.
- non-curable oligomer (C1) a polyoxyalkylene polyol is preferable, and a polyoxypropylene polyol is particularly preferable because the storage shear modulus of the adhesive layer tends to be low. Further, as the non-curable oligomer (C1), a polyoxyalkylene polyol having an oxypropylene group and an oxyethylene group may be used.
- Non-curable oligomer (C2) The non-curable oligomer (C) may be further blended with a non-curable oligomer (C2) having no hydroxyl group.
- the number average molecular weight of the non-curable oligomer (C2) is preferably 1,000 to 8,000. If the number average molecular weight of the non-curable oligomer (C2) is 1,000 or more, the non-curable oligomer (C2) is difficult to bleed out. If the number average molecular weight of the non-curable oligomer (C2) is 8,000 or less, it becomes easy to adjust the viscosity of the first composition to a range described later.
- non-curable oligomer (C2) examples include a compound in which the hydroxyl group of the non-curable oligomer (C1) is substituted with a group having no reactivity with the acryloyl group, and a high molecular weight polydiene.
- the polydiene examples include polybutadiene, polyisoprene, a water additive of polybutadiene, and polybutene.
- Examples of the compound in which the hydroxyl group of the non-curable oligomer (C1) is substituted with a group that is not reactive with the acryloyl group include polyoxyalkylene polyol alkoxylated products, monocarboxylic oxides, halogenated acetylated products, and esterified products. Can be mentioned.
- the curable oligomer (A) is a urethane acrylate oligomer synthesized using polyoxyalkylene polyol and polyisocyanate as raw materials
- the non-curable oligomer (C) is a polyoxyalkylene polyol. It is preferable in terms of compatibility.
- hydroxyl group-containing compound used as the raw material of the curable oligomer (A) and the hydroxyl group-containing compound used as the non-curable oligomer (C) are structural units having a common molecular chain (oxyalkylene). It is preferable that they have a partially common structure, such as having units and diene units, and have the same polarity. If the curable oligomer (A) and the non-curable oligomer (C) partially have the same molecular structure, the compatibility of the non-curable oligomer (C) in the first composition is further increased. .
- the curable oligomer (A) is a urethane acrylate oligomer synthesized using a polyoxypropylene polyol in which a part of the oxypropylene group is substituted with an oxyethylene group and a polyisocyanate as raw materials
- a non-curable oligomer (C ) Is a polyoxypropylene polyol having no oxyethylene group, and is a polyoxypropylene polyol having a molecular weight per hydroxyl group smaller than that of the polyol used in the curable oligomer (A).
- the following combinations are particularly preferable.
- the curable oligomer (A) is reacted with a polyoxyalkylene diol having an oxypropylene group and an oxyethylene group and a polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacted with a monomer (a1).
- photopolymerization initiator (D) examples include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators.
- phosphine oxide and thioxanthone photopolymerization initiators are preferable, and phosphine oxide is particularly preferable from the viewpoint of suppressing coloring after the photopolymerization reaction.
- Additives include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (ultraviolet absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion improvers (silane coupling agents) Etc.), pigments, dyes and the like.
- a polymerization inhibitor and a light stabilizer are preferable.
- the storage stability of the first composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the first composition can also be adjusted.
- Polymerization inhibitors include hydroquinone (2,5-di-tert-butylhydroquinone, etc.), catechol (p-tert-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene, and the like. Can be mentioned.
- the light stabilizer include ultraviolet absorbers (benzotriazole series, benzophenone series, salicylate series, etc.), radical scavengers (hindered amine series), and the like.
- examples of the antioxidant include hindered phenol compounds, phosphorus compounds, and sulfur compounds.
- the proportion of the low molecular weight polymerizable compound (B) in the first composition is preferably 1 to 80% by mass in the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 3 to 70% by mass is more preferable. If the ratio of a low molecular weight polymeric compound (B1) is more than the said lower limit, the storage stability of a 1st composition will become favorable, and the adhesiveness of an adhesion layer and a transparent surface material, and an adhesion layer and to-be-adhered Adhesion with compound (display panel, etc.) is improved.
- the proportion of the low molecular weight polymerizable compound (B2) is preferably 50% by mass or less of the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B) in the first composition.
- the mass% or less is more preferable.
- the monomer (a1) that has reacted with the isocyanate group of the prepolymer exists as a part of the curable oligomer (A), so that low molecular weight polymerization is performed. Not included in the ratio of the active compound (B).
- a low molecular weight polymerizable compound (however, which does not react with the prepolymer) added as a diluent as a diluent during or after the synthesis of the curable oligomer (A11) or the curable oligomer (A21) is low.
- the low molecular weight polymerizable compound is included in the ratio of the low molecular weight polymerizable compound (B).
- the proportion of the non-curable oligomer (C) is preferably 1 to 60% by mass in the first composition (100% by mass). If the ratio of a non-curable oligomer (C) is more than the said lower limit, a bubble will not remain easily between an adhesion layer and a to-be-bonded thing. If the ratio of a non-curable oligomer (C) is below the said upper limit, if a pressure sensitive adhesive layer fully hardens, it will become easy to peel a protective film from a pressure sensitive adhesive layer.
- the first composition contains a non-curable oligomer (C)
- curing is performed out of the total (100% by mass) of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C).
- the curable oligomer (A) is preferably 6 to 80% by mass
- the low molecular weight polymerizable compound (B) is preferably 3 to 70% by mass
- the non-curable oligomer (C) is preferably 1 to 60% by mass. More preferably, A) is 6 to 60% by mass, the low molecular weight polymerizable compound (B) is 3 to 55% by mass, and the non-curable oligomer (C) is 1 to 60% by mass.
- the blending amount of the photopolymerization initiator (D) in the first composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 0.1 to 5 parts by mass is more preferable.
- the compounding amount of the additive in the first composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). .
- the viscosity of the first composition is preferably 0.05 to 50 Pa ⁇ s, more preferably 1 to 20 Pa ⁇ s. If the viscosity of the first composition is 0.05 Pa ⁇ s or more, the application shape of the first composition is maintained when the adhesive layer is formed. If the viscosity of the first composition is 50 Pa ⁇ s or less, it is easy to supply the first composition to the surface of the transparent surface material, and the productivity of the transparent surface material with an adhesive layer is good.
- the weir is a portion made of a transparent resin formed by applying and curing a liquid curable resin composition for forming a weir.
- the thickness of the weir is slightly thicker than the thickness of the adhesive layer. Even if the surface of the adhesive layer is not flat and the thickness of the adhesive layer is not constant, the thickness of the weir is slightly larger than the thickness of the adhesive layer in at least a part of the area where the weir is adjacent to the adhesive layer It is preferable.
- the thickness of the weir is preferably approximately equal to the average thickness of the adhesive layer excluding the area where the weir and the adhesive layer are close to each other, or, as described above, 0.005 to 0.05 mm thicker than the thickness of the adhesive layer. More preferably, the thickness is 0.01 to 0.03 mm thick.
- the width of the weir is preferably narrow.
- the width of the weir is preferably 0.5 to 2 mm, more preferably 0.8 to 1.6 mm.
- the storage shear modulus at 35 ° C. of the weir is preferably larger than the storage shear modulus at 35 ° C. of the adhesive layer.
- the storage shear elastic modulus of the weir is larger than the storage shear elastic modulus of the adhesive layer, the object to be bonded is bonded at the periphery of the adhesive layer when the object to be bonded and the transparent surface material with the adhesive layer are bonded. Even if air bubbles remain at the interface between the adhesive layer and the adhesive layer, the air bubbles are not easily released to the outside, and become independent air bubbles.
- the pressure inside the bubbles that is, the reduced pressure of the reduced pressure atmosphere remains
- the pressure applied to the adhesive layer that is, the atmospheric pressure when the pressure is returned to the atmospheric pressure
- the thickness of the weir is slightly smaller than the thickness of the adhesive layer in at least a part of the region where the weir is close to the adhesive layer. It is easy to produce a transparent face material with a large adhesive layer.
- curable resin composition for weir formation examples include a composition containing a silicone resin (organopolysiloxane), a urethane oligomer, a urethane acrylate oligomer, and the like.
- a composition containing an oligomer (F) and a monomer (G) (hereinafter referred to as a second composition) is preferable from the viewpoints of flexibility and curing speed.
- the second composition may be a photocurable resin composition or a thermosetting resin composition.
- a 2nd composition it is preferable that it is a photocurable resin composition with which the photoinitiator (E) was further mix
- the second composition is a photocurable resin composition, a high temperature is not required for curing, so there is little risk of damage to the display panel due to high temperatures.
- the second composition may contain an additive as necessary. Moreover, in order to maintain the space
- the oligomer (F) is a compound having an addition polymerizable unsaturated double bond and a number average molecular weight of 30,000 to 100,000.
- Examples of the addition polymerizable unsaturated double bond of the oligomer (F) include an acryloyloxy group and a methacryloyloxy group.
- an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint that a curing rate is high and a highly transparent weir is obtained.
- the difference in the reactivity of the addition polymerizable unsaturated double bond between the oligomer (F) and the monomer (G) is reduced, and a homogeneous weir can be formed.
- the double bond is an acryloyloxy group and the addition polymerizable unsaturated double bond of the monomer (G) is a methacryloyloxy group.
- the number average molecular weight of the oligomer (F) is 30,000 to 100,000, preferably 40,000 to 80,000, more preferably 50,000 to 65,000. If the number average molecular weight of an oligomer (F) is in the said range, it will be easy to adjust the viscosity of a 2nd composition to the range mentioned later.
- the average number of addition polymerizable unsaturated double bonds of the oligomer (F) is preferably 1.8 to 4 from the viewpoint of the curability of the second composition and the mechanical properties of the weir.
- the oligomer (F) examples include a urethane oligomer having a urethane bond, a poly (meth) acrylate of a polyoxyalkylene polyol, and a poly (meth) acrylate of a polyester polyol.
- Urethane oligomers synthesized using polyols and polyisocyanates as raw materials are preferred from the viewpoint that the mechanical properties of the weir after curing, adhesion to the transparent surface material, and the like can be widely adjusted by molecular design of the urethane chain, which will be described later.
- the oligomer (F1) obtained by the synthesis method is more preferable.
- polyol polyoxyalkylene polyol is more preferable.
- Oligomer (F1) Since the oligomer (F1) having a number average molecular weight in the range of 30,000 to 100,000 has a high viscosity, it is difficult to synthesize by a normal method, and even if synthesized, it is difficult to mix with the monomer (G). Therefore, after synthesizing the oligomer (F1) by a synthesis method using the monomer (G) (the following monomer (G1) and monomer (G2)), the obtained product is used as it is as the second composition, or It is preferable that the obtained product is further diluted with a monomer (G) (the following monomers (G1) to monomer (G3), etc.) to be used as the second fat composition.
- a monomer (G) the following monomers (G1) to monomer (G3), etc.
- Monomer (G1) Monomer (G) that has an addition-polymerizable unsaturated double bond and does not have a group that reacts with an isocyanate group.
- Monomer (G2) Monomer (G) having an addition polymerizable unsaturated double bond and a group that reacts with an isocyanate group.
- Monomer (G3) Monomer (G) having an addition polymerizable unsaturated double bond and a hydroxyl group.
- the oligomer (F1) is obtained by the following synthesis method.
- polyol As a polyol, the thing similar to the polyol illustrated by the 1st composition is mentioned.
- the polyol may be the same as or different from the first composition, but the same is preferable.
- the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 2nd composition.
- a polyol may be used individually by 1 type and may use 2 or more types together.
- polyisocyanate examples include the same polyisocyanates exemplified in the first composition.
- the polyisocyanate may be the same as or different from the first composition, but the same is preferable.
- Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
- the monomer (G) is a compound having an addition polymerizable unsaturated double bond and a molecular weight of 125 to 600.
- Examples of the addition polymerizable unsaturated double bond of the monomer (G) include an acryloyloxy group and a methacryloyloxy group.
- an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint that a curing rate is high and a highly transparent weir is obtained.
- the difference in the reactivity of the addition polymerizable unsaturated double bond between the oligomer (F) and the monomer (G) is reduced, and a homogeneous weir can be formed.
- the double bond is an acryloyloxy group and the addition polymerizable unsaturated double bond of the monomer (G) is a methacryloyloxy group.
- the molecular weight of the monomer (G) is 125 to 600, preferably 140 to 400, more preferably 150 to 350. If the molecular weight of the monomer (G) is 125 or more, volatilization of the monomer (G) when manufacturing the display device can be suppressed. If the molecular weight of a monomer (G) is 600 or less, the solubility of the monomer (G) with respect to the high molecular weight oligomer (F) can be improved, and the viscosity adjustment as a 2nd composition can be performed suitably.
- the monomer (G) may contain the monomer (G1) used as a diluent in the synthesis method of the oligomer (F1). Moreover, the unreacted monomer (G2) used for the synthesis method of the oligomer (F1) may be included as the monomer (G). Moreover, it is preferable that a monomer (G) contains a monomer (G3) from the point of the adhesiveness of a transparent surface material and a weir, and the solubility point of an additive.
- Monomers (G1) include alkyl (meth) acrylates having an alkyl group of 8 to 22 carbon atoms (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-behenyl (meth) acrylate, etc.)), fat Examples include (meth) acrylates having a cyclic hydrocarbon group (such as isobornyl (meth) acrylate and adamantyl (meth) acrylate).
- Monomer (G2) examples include monomers having active hydrogen (hydroxyl group, amino group, etc.) and an addition polymerizable unsaturated double bond.
- Specific examples of the monomer (G2) include hydroxyalkyl (meth) acrylates having a C2-C6 hydroxyalkyl group (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl). (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.).
- a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferable.
- Monomers (G3) include hydroxy methacrylates having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl). Methacrylate) and the like are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.
- photopolymerization initiator (E) examples include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators.
- the photopolymerization initiator (E) acetophenone-based, ketal-based, and benzoin ether-based photopolymerization initiators are preferable.
- a phosphine oxide-based photopolymerization initiator is more preferable from the viewpoint of the absorption wavelength region.
- additives As an additive, the thing similar to what was mentioned by the 1st composition is mentioned.
- a polymerization inhibitor and a light stabilizer are preferable.
- the storage stability of the second composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the second composition can also be adjusted.
- the proportion of the monomer (G) in the second composition is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, out of the total (100% by mass) of the oligomer (F) and the monomer (G), 25 More preferably, it is 40% by mass.
- the proportion of the monomer (G) is 15% by mass or more, the curability of the second composition and the adhesion between the transparent surface material and the weir are good. If the ratio of a monomer (G) is 50 mass% or less, it will be easy to adjust the viscosity of a 2nd composition to 500 Pa.s or more.
- the blending amount of the photopolymerization initiator (E2) in the second composition is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts per 100 parts by mass in total of the oligomer (F) and the monomer (G). Part by mass is more preferable.
- the total amount of additives in the second composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the oligomer (F) and the monomer (G).
- the viscosity of the second composition is preferably 500 to 3000 Pa ⁇ s, more preferably 800 to 2500 Pa ⁇ s, and still more preferably 1000 to 2000 Pa ⁇ s. If the viscosity of the second composition is 500 Pa ⁇ s or more, the shape of the weir before curing can be maintained for a relatively long time, and the height of the weir before curing can be sufficiently maintained. If the viscosity of the second composition is 3000 Pa ⁇ s or less, the weir before curing can be formed by coating.
- the viscosity of the second composition is less than 500 Pa ⁇ s
- the second composition is a photocurable resin composition, by irradiating light immediately after coating, What is necessary is just to let the viscosity of a 2nd composition be the said preferable range.
- the viscosity at the time of application of the second composition is preferably less than 500 Pa ⁇ s, and more preferably 200 Pa ⁇ s or less.
- the protective film is required not to adhere firmly to the adhesive layer. Therefore, as the protective film, a film having a relatively low adhesion to the adhesive layer, such as polyethylene, polypropylene, and fluorine resin, is preferable.
- the protective film is preferably a self-adhesive protective film in which one surface of a base film having relatively low adhesion is an adhesive surface.
- the adhesive strength of the adhesive surface of the protective film is preferably 0.01 to 0.1 N, preferably 0.02 to 0.06 N in a 50 mm wide test specimen in a 180 degree peel test with a peel rate of 300 mm / min. More preferred. If the said adhesive force is more than the said lower limit, the bonding to a support surface material is possible. If the adhesive strength is not more than the upper limit value, it is easy to peel the protective film from the support surface material.
- the thickness of the protective film varies depending on the resin used, but when a relatively flexible film such as polyethylene or polypropylene is used, it is preferably 0.04 to 0.2 mm, more preferably 0.06 to 0.1 mm. If the thickness of a protective film is more than the said lower limit, when peeling a protective film from an adhesion layer, a deformation
- FIG. 1 is a cross-sectional view showing a first embodiment of a transparent surface material with an adhesive layer of the present invention.
- the transparent surface material 1 with an adhesive layer includes a transparent surface material 10, a light shielding printing portion 12 (light shielding portion) formed on the peripheral edge of the surface of the transparent surface material 10, and a transparent surface on the side where the light shielding printing portion 12 is formed. It has a layered adhesive layer 14 formed on the surface of the material 10 and a peelable protective film 16 covering the surface of the adhesive layer 14.
- a display apparatus can be manufactured by peeling the protective film 16 from the transparent surface material 1 with an adhesion layer, and bonding with the transparent surface material 1 with an adhesion layer and a display panel.
- the transparent surface material 10 is provided on the image display surface side (that is, the viewing side) of the display panel described later to protect the display panel.
- the transparent face material 10 may be provided with an antireflection layer on the surface opposite to the side on which the adhesive layer 14 is formed. Further, depending on the purpose, a part or the whole of the transparent face material 10 is colored, or a part or the whole of the surface of the transparent face material 10 is polished to form a glass to scatter light, or the surface of the transparent face material 10 is scattered. Further, a minute unevenness or the like may be formed on a part or the whole of the light to refract or reflect the transmitted light. Further, a colored film, a light scattering film, a photorefractive film, a light reflecting film, or the like may be bonded to a part or the whole of the surface of the transparent surface material 10.
- the shape of the transparent surface material 10 is preferably rectangular in order to match the outer shape of the display device. Depending on the outer shape of the display device, it is possible to use a transparent surface material that covers the entire display surface of the display panel and has a shape that includes a curve in the outer shape.
- the size of the transparent face material 10 may be appropriately set according to the outer shape of the display device.
- the thickness of the transparent face material 10 is 0.5 to 0.5 in the case of a glass plate from the viewpoint of mechanical strength and transparency. It is preferably 25 mm. For applications such as television receivers and PC displays used indoors, 1 to 6 mm is preferable from the viewpoint of reducing the weight of the display device, and for public display applications installed outdoors, 3 to 20 mm is preferable. When chemically strengthened glass is used, the thickness of the glass plate is preferably about 0.5 to 1.5 mm in terms of strength. In the case of a transparent resin plate, 2 to 10 mm is preferable.
- the light-shielding printing unit 12 hides wiring members and the like connected to the display panel so that areas other than the image display area of the display panel, which will be described later, are not visible from the transparent surface material 10 side.
- the light-shielding printing unit 12 can be formed on the surface on which the adhesive layer 14 is formed or on the opposite surface. In terms of reducing the parallax between the light-shielding printing unit 12 and the image display area, it is preferable to form the surface on the side where the adhesive layer 14 is formed.
- the transparent surface material 10 is a glass plate, it is preferable to use ceramic printing containing a black pigment for the light shielding printing portion 12 because of high light shielding properties.
- the display panel wiring member or the like has a structure that cannot be seen from the side of the display panel observation, or is concealed by another member such as a housing of the display device, or a bonded object and an adhesive layer other than the display panel
- the light shielding printing portion 12 may not be formed on the transparent face material 10.
- the adhesive layer 14 is a layer made of a transparent resin formed by curing the first composition described above.
- the protective film 16 As the protective film 16, a film having a relatively low adhesiveness to the adhesive layer such as the above-described polyethylene, polypropylene, and fluorine resin is used.
- FIG. 2 is a cross-sectional view showing a second embodiment of the transparent surface material with an adhesive layer of the present invention.
- the transparent surface material 2 with the adhesive layer includes a transparent surface material 10, a light shielding printing portion 12 (light shielding portion) formed on the peripheral edge of the surface of the transparent surface material 10, and a transparent surface on the side where the light shielding printing portion 12 is formed.
- the display device After peeling off the protective film 16 from the transparent surface material 2 with the adhesive layer, the display device can be produced by pasting the transparent surface material 2 with the adhesive layer and the display panel.
- symbol is attached
- the weir 15 is a portion made of a transparent resin obtained by curing the above-described second composition.
- the transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer, and the hydroxyl group concentration and the urethane bond concentration in the adhesive layer may be within a specific range. The thing is not limited.
- the concentration of hydroxyl groups in the adhesive layer is 600 ⁇ 10 ⁇ 6 mol / g or less, and the concentration of urethane bonds in the adhesive layer is 150 ⁇ Since it is 10 ⁇ 6 mol / g or less, the bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive layer can rapidly disappear when it is bonded to the object to be bonded (display panel or the like). Further, since the concentration of the hydroxyl group in the adhesive layer is 100 ⁇ 10 ⁇ 6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded are good. Become.
- the manufacturing method of the transparent surface material with the adhesion layer of this invention has the following process ((alpha)), the following process ((beta)), and the following process ((gamma)). This order is preferable as the order of the following process ( ⁇ ), the following process ( ⁇ ), and the following process ( ⁇ ).
- ( ⁇ ) A step of supplying a liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
- the method for producing a transparent surface material with an adhesive layer of the present invention includes a method for producing a transparent surface material with an adhesive layer not having a weir (for example, the transparent surface material with an adhesive layer of the first embodiment), and an adhesive layer having a weir. It is divided into the manufacturing method of a transparent surface material (for example, the transparent surface material with the adhesion layer of 2nd Embodiment).
- the step ( ⁇ 1) may be the following step ( ⁇ 1a) or the following step ( ⁇ 1b).
- Supply of the adhesive layer-forming curable resin composition, a small area for installing a device necessary for curing, and the periphery of the adhesive layer-forming curable resin composition supplied to the surface of the transparent surface The step ( ⁇ 1a) is preferable from the viewpoint that the peripheral portion can be prevented from being thinned by spreading outward.
- ( ⁇ 1a) Partially curing the curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material while supplying the liquid curable resin composition for forming an adhesive layer to the surface of the transparent surface material And a step of forming a partially cured product layer.
- ( ⁇ 1b) A liquid adhesive layer-forming curable resin composition is supplied to the surface of the transparent surface material in layers, and after forming the adhesive layer-forming curable resin composition, the adhesive layer-forming curable resin composition A step of partially curing the layer of the product to form a layer of the partially cured product.
- the supply of the curable resin composition for forming an adhesive layer is performed using a die coater, a knife coater or the like.
- the curable resin composition for forming an adhesive layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED).
- a light source such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED.
- Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the side where the curable resin composition for forming an adhesive layer is supplied.
- curing of the adhesive layer forming curable resin composition is performed by heating.
- the storage shear modulus at 35 ° C. of the partially cured product layer is 1/200 to 1/5 of the storage shear modulus at 35 ° C. of the target adhesive layer. If the storage shear modulus at 35 ° C. of the partially cured product layer is equal to or higher than the lower limit, the shape of the partially cured product layer does not collapse when the protective film is stacked. If the storage shear modulus at 35 ° C. of the partially cured product layer is less than or equal to the above upper limit, the adhesion with the protective film will be sufficiently high.
- a protective film is overlaid on the surface of the partially cured product layer, and the surface of the partially cured product layer is covered with the protective film.
- the superposition may be performed under atmospheric pressure, or may be performed under a reduced-pressure atmosphere as in the step ( ⁇ 2) described later. After the overlapping, it is preferable to gradually press-bond from the end of the partially cured product layer so that the shape of the partially cured product layer does not collapse.
- a laminator may be used for the pressure bonding.
- the partially cured product layer is further cured to form an adhesive layer.
- the partially cured product layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED). Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the protective film side.
- a thermosetting resin composition the partially cured product layer is cured by heating.
- a line-like shape is arranged downstream of the die coater 62 in the moving direction of the transparent face material 10 so that the longitudinal direction is orthogonal to the moving direction of the transparent face material 10.
- the LED light source 64 is irradiated with linear light (ultraviolet light or short-wavelength visible light), and the first composition 18 supplied to the surface of the transparent surface material 10 is cured to form the partially cured material layer 20. .
- the protective film 16 is placed on the surface of the partially cured product layer 20 under atmospheric pressure, and from the end of the partially cured product layer 20 using a laminator (not shown). The protective film 16 is gradually pressure-bonded to cover the surface of the partially cured product layer 20 with the protective film 16.
- the partially cured product layer 20 is irradiated with light (ultraviolet rays or short-wavelength visible light) from the protective film 16 side, and the partially cured product layer 20 is further cured to form the adhesive layer 14. Thereby, the transparent surface material 1 with the adhesion layer shown in FIG. 1 is obtained.
- Method for producing transparent surface material with adhesive layer having weir As a manufacturing method of the transparent surface material with an adhesive layer having a weir, for example, a method having the following step ( ⁇ 21), the following step ( ⁇ 22), the following step ( ⁇ 2), the following step ( ⁇ 21), and the following step ( ⁇ 22). Can be mentioned.
- ( ⁇ 21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
- ( ⁇ 22) A step of supplying the adhesive layer-forming curable resin composition to the region surrounded by the weir.
- a support surface material with a protective film is placed on the layer of the curable resin composition for forming an adhesive layer under a reduced pressure atmosphere, and the protective film is in contact with the surface of the layer of the curable resin composition for forming an adhesive layer.
- ( ⁇ 22) A step of peeling the support surface material from the protective film after the step ( ⁇ 21).
- a liquid weir-forming curable resin composition is applied to the periphery of the surface of the transparent face material to form a weir.
- the application is performed using a printing machine, a dispenser, or the like.
- the weir may be in an uncured state or a partially cured semi-cured state.
- the curable resin composition for weir formation is a photocurable composition
- partial curing of the weir is performed by light irradiation.
- the photocurable resin composition is partially cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.).
- a liquid adhesive layer forming curable resin composition is supplied to a region surrounded by the weir.
- the supply amount of the curable resin composition for forming the adhesive layer is such that the space formed by the weir, the transparent surface material and the protective film is filled with the curable resin composition for forming the adhesive layer, and the transparent surface material and the protective film
- the amount is set in advance so that the interval is a predetermined interval (that is, the adhesive layer has a predetermined thickness). At this time, it is preferable to consider in advance volume reduction due to curing shrinkage of the curable resin composition for forming an adhesive layer.
- the amount is preferably such that the thickness of the curable resin composition for forming an adhesive layer is slightly larger than the predetermined thickness of the adhesive layer.
- the supply method include a method in which the transparent face material is placed flat and the adhesive layer-forming curable resin composition is supplied in the form of dots, lines or planes by a supply means such as a dispenser or a die coater.
- the transparent surface material supplied with the curable resin composition for forming the adhesive layer is put into a decompression device, and the adhesive layer is formed on the fixed support disk in the decompression device.
- the transparent face material is laid flat so that the surface of the curable resin composition is on top.
- a moving support mechanism that can move in the vertical direction is provided in the upper part of the decompression device, and a support surface material (such as a glass plate) is attached to the moving support mechanism.
- a protective film is bonded to the lower surface of the support surface material.
- the supporting face material is placed above the transparent face material and at a position not in contact with the curable resin composition for forming the adhesive layer. That is, the curable resin composition for forming an adhesive layer on the transparent surface material and the protective film bonded to the surface of the support surface material are opposed to each other without being brought into contact with each other.
- the inside of the pressure reducing device is depressurized to obtain a predetermined reduced pressure atmosphere.
- the support surface material supported by the moving support mechanism is moved downward, and the support surface material with a protective film is placed on the first composition on the transparent surface material.
- this superposition is referred to as a laminate.
- the adhesive layer forming curable resin composition is sealed in the surface surrounded by the surface of the transparent surface material, the surface of the protective film bonded to the support surface material, and the weir.
- the adhesive layer-forming curable resin composition is spread by the weight of the supporting surface material, the pressure from the moving support mechanism, etc., and the space is filled with the adhesive layer-forming curable resin composition.
- An uncured adhesive layer is formed. Thereafter, when exposed to a high pressure atmosphere in the step ( ⁇ 21), an uncured adhesive layer with few or no bubbles is formed.
- the reduced pressure atmosphere at the time of superposition is preferably 1 kPa or less, more preferably 10 to 300 Pa, and further preferably 15 to 100 Pa. If the reduced-pressure atmosphere is extremely low, each component (curable compound, photopolymerization initiator, polymerization inhibitor, chain transfer agent, light stabilizer, etc.) contained in the curable resin composition for forming an adhesive layer will be adversely affected. There is a risk of giving. For example, if the reduced-pressure atmosphere is extremely low pressure, each component may be vaporized, and it may take time to provide the reduced-pressure atmosphere.
- the time from when the transparent surface material and the support surface material are overlapped to when the reduced pressure atmosphere is released is not particularly limited, and even after the reduced pressure atmosphere is released immediately after sealing the curable resin composition for forming the adhesive layer.
- the reduced pressure state may be maintained for a predetermined time.
- the laminate After releasing the reduced pressure atmosphere in the step ( ⁇ 2), as a step ( ⁇ 21), the laminate is placed in a higher pressure atmosphere than in the step ( ⁇ 2).
- a pressure atmosphere higher than the step ( ⁇ 2) a pressure atmosphere of 50 kPa or more is preferable.
- the pressure is increased in the direction in which the transparent surface material and the support surface material are in close contact with each other. Therefore, if bubbles exist in the sealed space in the laminate, the uncured adhesive layer flows into the bubbles, and the entire sealed space is uniformly filled with the uncured adhesive layer.
- the time from when the laminate is placed in a higher pressure atmosphere than in the step ( ⁇ 2) to the start of curing of the uncured adhesive layer (hereinafter referred to as “high pressure holding time”) is not particularly limited.
- the time required for the process becomes the high pressure holding time. Therefore, if there are no air bubbles in the sealed space of the laminate when placed in an atmospheric pressure atmosphere, or if the air bubbles disappear during the process, the uncured adhesive layer can be cured immediately. it can.
- the laminate is held under a higher pressure atmosphere than the step ( ⁇ 2) until the bubbles disappear.
- the high-pressure holding time may be a long time of one day or longer, but is preferably within 6 hours from the viewpoint of production efficiency, more preferably within 1 hour, and particularly within 10 minutes from the viewpoint of further increasing production efficiency. preferable.
- the adhesive layer and the weir are formed by curing the uncured adhesive layer and the uncured or semi-cured weir.
- the uncured or semi-cured weir may be cured simultaneously with the curing of the uncured adhesive layer, or may be cured in advance before the uncured adhesive layer is cured.
- the uncured adhesive layer and the uncured or semi-cured weir are made of a photocurable composition, they are cured by irradiation with light.
- the photocurable resin composition is cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.).
- a light-shielding printing part is formed on the peripheral edge of the transparent surface material, or a transparent resin film on which an antireflection layer is provided on the transparent surface material and an antireflection layer is formed, or the antireflection film and its transparent
- an adhesive layer or the like provided between the face material does not transmit ultraviolet rays, light is irradiated from the support face material side.
- the support surface material is peeled off from the protective film, whereby an adhesive layer having sufficient adhesive strength is formed in advance on the transparent surface material, and bubbles are generated at the interface between the transparent surface material and the adhesive layer.
- a transparent surface material with an adhesive layer in which is sufficiently suppressed can be obtained.
- the second composition is applied by a dispenser (not shown) or the like along the light shielding printing portion 12 at the peripheral edge of the transparent face material 10 to form an uncured weir 22.
- the first composition 26 is supplied to a rectangular region 24 surrounded by the uncured weir 22 of the transparent surface material 10.
- the supply amount of the first composition 26 is set in advance so that the space sealed by the uncured weir 22, the transparent face material 10, and the protective film 16 (see FIG. 10) is filled with the first composition 26. Is set.
- the first composition 26 is supplied by placing the transparent surface material 10 flat on the lower platen 28 and moving the first composition 26 into a linear or belt shape by a dispenser 30 that moves in the horizontal direction. Or it implements by supplying in a dot form.
- the dispenser 30 is horizontally movable in the entire range of the region 24 by a known horizontal movement mechanism including a pair of feed screws 32 and a feed screw 34 orthogonal to the feed screw 32.
- a die coater may be used.
- the transparent surface material 10 and the support surface material 36 with the protective film 16 are carried into the decompression device 38.
- An upper surface plate 42 having a plurality of suction pads 40 is disposed in the upper portion of the decompression device 38, and a lower surface plate 44 is disposed in the lower portion.
- the upper surface plate 42 can be moved in the vertical direction by an air cylinder 46.
- the support surface material 36 is attached to the suction pad 40 with the surface to which the protective film 16 is bonded facing down.
- the transparent surface material 10 is fixed on the lower surface plate 44 with the surface to which the first composition 26 is supplied facing up.
- the air in the decompression device 38 is sucked by the vacuum pump 48.
- the atmospheric pressure in the decompression device 38 reaches, for example, a reduced pressure atmosphere of 15 to 100 Pa
- the transparent surface material waiting underneath while the support surface material 36 is adsorbed and held by the adsorption pad 40 of the upper surface plate 42. 10
- the air cylinder 46 is operated and lowered.
- the transparent surface material 10 and the support surface material 36 with the protective film 16 are piled up through the uncured weir 22.
- the transparent body 10, the protective film 16, and the uncured weir 22 constitute a laminated body in which the uncured adhesive layer made of the first composition 26 is sealed, and the laminated body is formed for a predetermined time in a reduced-pressure atmosphere. Hold.
- the laminate is taken out from the decompression device 38.
- the surface of the laminate on the transparent face material 10 side and the surface on the support face material 36 side are pressed by atmospheric pressure, and the uncured adhesive layer in the sealed space becomes a transparent face material. 10 and the support surface material 36 are pressurized. By this pressure, the uncured adhesive layer in the sealed space flows, and the entire sealed space is uniformly filled with the uncured adhesive layer.
- the uncured weir 22 and the uncured adhesive layer are irradiated with light (ultraviolet rays and visible light having a short wavelength) from the support surface material 36 side, and the uncured weir 22 and the uncured adhesive layer inside the laminate are then irradiated. Is cured to form the adhesive layer 14 and the weir 15.
- the method for producing a transparent surface material with an adhesive layer of the present invention is a method for producing the transparent surface material with an adhesive layer of the present invention, as long as it is a method having a step ( ⁇ ) and a step ( ⁇ ). It is not limited to the manufacturing method of the transparent surface material with an adhesion layer.
- the peripheral edge portion of the protective film of the transparent surface material with the adhesive layer may be airtightly bonded to the transparent surface material over the entire circumference under reduced pressure conditions.
- the peripheral portion of the protective film 16 of the transparent surface material 1 with the adhesive layer shown in FIG. 1 is placed at any position (side surface, lower surface, upper surface, etc.) of the transparent surface material 10 over the entire circumference under reduced pressure conditions.
- the adhesive layer 14 is hermetically wrapped in the protective film 16, so it is possible to reliably prevent outside air from being mixed into the adhesive layer 14.
- the method for producing the transparent surface material with an adhesive layer of the present invention comprising the step ( ⁇ ) and the step ( ⁇ ), When bonded to the object to be bonded, it is possible to produce a transparent surface material with an adhesive layer in which bubbles remaining at the interface between the object to be bonded and the adhesive layer can quickly disappear.
- FIG. 11 is a cross-sectional view illustrating an example of the display device of the present invention.
- the display device 3 includes the display panel 50 and the transparent surface material 2 with the adhesive layer bonded to the display panel 50 so that the adhesive layer 14 contacts the display panel 50.
- the display device 3 is connected to the transparent surface material 10, the display panel 50, the adhesive layer 14 sandwiched between the transparent surface material 10 and the display panel 50, the weir 15 surrounding the adhesive layer 14, and the display panel 50.
- a flexible printed wiring board 60 (FPC) on which a driving IC for operating the display panel 50 is mounted.
- FPC flexible printed wiring board 60
- Display panel As shown in FIG. 11, in the display panel 50, a transparent substrate 52 provided with a color filter and a transparent substrate 54 provided with a TFT are bonded with a liquid crystal layer 56 interposed therebetween, and this is sandwiched between a pair of polarizing plates 58. It is an example of the liquid crystal panel of a structure.
- the surface treatment may be performed only on the peripheral edge or on the entire surface of the face material.
- Examples of the surface treatment method include a treatment method using an adhesion primer or the like which can be processed at a low temperature.
- the thickness of the display panel 50 is about 0.4 to 4 mm in the case of a liquid crystal panel operated by TFT, and is often about 0.2 to 3 mm in the case of an EL panel.
- the shape of the display panel 50 is generally a rectangle.
- the dimensions of the transparent surface material 10 and the display panel 50 may be substantially equal, or the transparent surface material 10 may be made slightly larger than the display panel 50 in view of the relationship with the other housing that houses the display device. Conversely, the transparent surface material 10 may be slightly smaller than the display panel 50 depending on the structure of another casing.
- the display apparatus of this invention should just be what the transparent surface material with the adhesion layer of this invention was bonded by the display panel, and is not limited to the thing of the example of illustration.
- the display panel is not limited to the liquid crystal panel shown in FIG.
- the display panel changes in optical characteristics by an external electric signal between a pair of electrodes, at least one of which is a transparent electrode, or between a substrate having a plurality of electrode pairs formed in the same plane and a transparent substrate.
- the display material is sandwiched.
- the display panel has a structure in which a pair of face materials, at least one of which is a transparent substrate, is bonded, and is arranged so that the transparent substrate side is in contact with the adhesive layer.
- an optical film such as a polarizing plate or a retardation plate may be provided on the outermost layer side of the transparent substrate on the side in contact with the adhesive layer.
- the adhesive layer is in a state of joining the optical film on the display panel and the transparent surface material.
- the protective film (protective material) is peeled from the transparent surface material with the adhesive layer of the present invention, and then the display panel and the transparent surface material with the adhesive layer are bonded to the display panel. Laminate to touch.
- the manufacturing method of the display device may be a method including steps S1 and S2 described below.
- Step S1 Protective film peeling step
- the protective film is peeled from the transparent surface material with the adhesive layer, which is covered with the protective film.
- the protective film may be peeled in the air or in a reduced pressure atmosphere.
- the transparent surface material with the adhesive layer can be stored in a reduced pressure atmosphere without being exposed to the atmosphere until the transparent surface material with the adhesive layer is transferred to the inside of the vacuum container used in the step S2.
- It is preferable to carry out the peeling of the protective film in the air in that it is not necessary to prepare a vacuum container for the protective film peeling step. After the protective film is peeled off, it is preferable to immediately perform the next step S2.
- Process S2 Pasting process
- the bonding apparatus the display panel and the transparent surface material with the adhesive layer are bonded together in a state where the adhesive layer is in contact with the display panel.
- the reduced pressure atmosphere at the time of pasting is preferably 20 kPa or less, more preferably 15 to 0.5 kPa, and even more preferably 10 to 0.2 kPa. If the degree of decompression is less than or equal to the above upper limit, bubbles are unlikely to remain, and if the degree of decompression is greater than or equal to the lower limit, a large decompression device is not required.
- the time from when the display panel and the transparent surface material with the adhesive layer are overlapped to when the reduced pressure atmosphere is released is short. For example, it is preferably within 1 minute, and more preferably within 10 seconds.
- the adhesive layer that is not fully cured is irradiated with light again or heated to accelerate the curing of the adhesive layer, and the adhesive layer is cured. May be stabilized.
- the transparent surface material with the adhesive layer has flexibility
- the transparent surface material with the adhesive layer is curved so that the surface side on which the adhesive layer is formed of the transparent surface material with the adhesive layer is convex, and the adhesive layer
- the attached transparent surface material may be bonded by a method of gradually overlapping the display panel from one end side to the other end side. According to this method, since the gas existing in the space between the transparent surface material with the adhesive layer and the display panel is pushed out from one end side to the other end side, the bonding is performed, so the interface between the display panel and the adhesive layer Air bubbles are less likely to be generated.
- Process P1 Volume reduction by bonding differential pressure
- the process P1 After the display panel and the transparent surface material with the adhesive layer are bonded in a reduced pressure atmosphere, when the pressure is returned to the normal pressure atmosphere, the pressure inside the bubbles in the reduced pressure state and the adhesive layer from the outside
- a differential pressure from the applied pressure that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere
- the period of the process P1 is, for example, about several seconds. That is, the volume of the bubble is rapidly reduced after a few seconds from the time when the pressure is returned to the atmospheric pressure.
- Process P2 Volume reduction by absorption of gas in bubbles into the adhesive layer
- Process P2 is a process in which the volume of bubbles is reduced by the gas confined in the bubbles being absorbed and dissolved in the adhesive layer in contact with the bubbles.
- the period of the process P2 is about several minutes to several tens of minutes, for example.
- the rate of bubble volume reduction in process P2 is slower than the rate of bubble volume reduction in process P1.
- the period of the process P3 is, for example, several hours or more.
- the speed of the bubble volume reduction in the process P3 depends on the diffusion rate of the gas in the adhesive layer, and is therefore slower than the speed of the bubble volume reduction in the process P2. The bubbles disappear almost completely through the process P3.
- bubbles (M1 and M2 in FIG. 12) are generated at the interface between the display panel 50 and the adhesive layer 14.
- the conventional transparent surface material with an adhesive layer tends to require a long time for the disappearance of bubbles when stored for a long time after production.
- the bubbles disappear in a short time even when used for pasting with an object to be pasted after a long period of time has passed since the manufacture.
- the reason why the bubbles disappear in a short time when the transparent surface material with an adhesive layer of the present invention is used can be inferred as follows.
- the adhesive layer with transparent surface material of the present invention the concentration of hydroxyl groups in the adhesive layer is not more than 600 ⁇ 10 -6 mol / g, the concentration of urethane linkages in the adhesive layer, 0.99 ⁇ 10 -6 mol / g or less. Therefore, the pressure-sensitive adhesive layer has a weak cohesive force and facilitates gas diffusion into the pressure-sensitive adhesive layer. As a result, the processes P2 and P3 are accelerated, and as a result, the remaining bubbles disappear in a short time.
- the manufacturing method of the display device of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are brought into contact with the display panel in a reduced pressure atmosphere. Any method can be used as long as it is laminated and bonded, and the production method described above is not limited.
- the gas content of the adhesive layer is reduced by placing the adhesive layer under reduced pressure conditions in the manufacturing process of the transparent face material with the adhesive layer of the second embodiment.
- the process by which the gas content of the adhesion layer decreases may be any time.
- the transparent surface material with an adhesive layer may be bonded to a coordinate input device such as a touch panel.
- the transparent surface material may be a substrate with a transparent electrode that constitutes a touch panel portion in a display device with a touch panel.
- An adhesive layer can also be formed on both surfaces of a substrate with a transparent electrode, and a transparent surface material and a display panel can be bonded via a substrate with a transparent electrode having an adhesive layer formed on both surfaces.
- the pressure-sensitive adhesive sheet of the present invention comprises a cured product of a curable resin composition for forming a pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet with a protective film further having a peelable protective film on one surface or both surfaces of the pressure-sensitive adhesive sheet, if necessary.
- the pressure-sensitive adhesive sheet is obtained by allowing the pressure-sensitive adhesive layer in the above-described transparent surface material with a pressure-sensitive adhesive layer to exist alone without the transparent surface material. Therefore, the characteristics and material of the pressure-sensitive adhesive sheet, and preferred embodiments are the same as those of the pressure-sensitive adhesive layer described above, and detailed description thereof is omitted.
- the pressure-sensitive adhesive sheet can be produced by a production method similar to the production method of the transparent surface material with an adhesive layer, for example, by using a protective film or a support surface material with a protective film instead of the transparent surface material.
- the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet layer is 600 ⁇ 10 ⁇ 6 mol / g or less, and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is 150 ⁇ 10 ⁇ 6. Since it is mol / g or less, when it bonds with a to-be-bonded object (transparent surface material, a display panel, etc.), the bubble which remain
- the concentration of the hydroxyl group in the pressure-sensitive adhesive sheet is 100 ⁇ 10 ⁇ 6 mol / g or more, the adhesion between the pressure-sensitive adhesive sheet and the object to be bonded (for example, a transparent surface material, a display panel, etc.) becomes good. .
- Examples 1, 2, 4, and 5 are examples, and examples 3 and 6 are comparative examples.
- the transparent surface material, the object to be bonded, the support surface material with a protective film, the curable oligomer (A), the non-curable oligomer (C), the first composition, and the second composition in each example are prepared as follows. It is a thing.
- Transparent surface material Transparent face material (1): Printed with ink containing a black pigment so that the translucent portion is 218 mm long and 168 mm wide at the periphery of one surface of a soda-lime glass plate having a length of 240 mm, a width of 190 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (1).
- Transparent face material (2) Printed with ink containing a black pigment so that the translucent portion is 85 mm long and 85 mm wide on one surface of a soda lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (2).
- Article to be bonded A polarizing plate with an adhesive layer (Polatechno Co., Ltd., KN-18240T) is bonded to one surface of a soda lime glass plate having a length of 220 mm, a width of 170 mm, and a thickness of 1.1 mm, and a liquid crystal panel is substituted. Compound (1) was obtained.
- Adhesive layered polarizing plate (Polatechno KN-18240T) is bonded to one side of a soda lime glass plate with a length of 90 mm, a width of 90 mm, and a thickness of 2 mm. It was set as thing (2).
- a protective film manufactured by Mitsui Chemicals Tosero Co., Ltd., Puretect
- a support surface material made of a soda-lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm.
- (Registered Trademark) VLH-9) was bonded using a rubber roll so that the adhesive surface of the protective film was in contact with the glass to produce a support surface material with a protective film.
- UA-1 Bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 18000) and isophorone diisocyanate are mixed at a molar ratio of 4 to 5, and obtained by reacting at 70 ° C. in the presence of a tin compound catalyst. 2-hydroxyethyl acrylate was added to the resulting prepolymer at a molar ratio of prepolymer and 2-hydroxyethyl acrylate of approximately 1: 2, and reacted at 70 ° C. to obtain a urethane acrylate oligomer (hereinafter referred to as UA-). 1)).
- the average number of addition polymerizable unsaturated double bonds of UA-1 was 2, the number average molecular weight was about 73,000, and the viscosity at 25 ° C. was about 250 Pa ⁇ s.
- UA-2 A urethane acrylate oligomer (hereinafter referred to as UA-2) was obtained in the same manner as UA-1, except that bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) was used.
- the average number of addition polymerizable unsaturated double bonds of UA-2 was 2, the number average molecular weight was about 41,000, and the viscosity at 25 ° C. was about 250 Pa ⁇ s.
- UA-3 A urethane acrylate oligomer (hereinafter referred to as UA-3) is produced in the same manner as UA-1, except that a bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) is used. ) The average number of addition polymerizable unsaturated double bonds of UA-3 was 2, the number average molecular weight was about 17,300, and the viscosity at 25 ° C. was about 250 Pa ⁇ s.
- UA-4 Bifunctional polypropylene glycol whose molecular terminal is modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and hexamethylene diisocyanate are mixed at a molar ratio of 6: 7, and then isobornyl acrylate (Osaka Organic Chemical Industry) After dilution with IBXA, a prepolymer was obtained by reaction at 70 ° C. in the presence of a tin catalyst.
- a urethane acrylate oligomer (UA-4) (hereinafter referred to as UA-4) was obtained.
- the average number of addition polymerizable unsaturated double bonds of UA-4 was 2, the number average molecular weight was 55000, and the viscosity at 60 ° C. was 580 Pa ⁇ s.
- UA-5 Monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) and 2-acryloyloxyethyl isocyanate are mixed at a molar ratio of 1: 1, and in the presence of a tin compound catalyst, 70 ° C. To obtain a urethane acrylate oligomer (hereinafter referred to as UA-5).
- the average number of addition polymerizable unsaturated double bonds of UA-5 was 1, the number average molecular weight was about 10100, and the viscosity at 25 ° C. was about 7 Pa ⁇ s.
- UA-6 A urethane acrylate oligomer (hereinafter referred to as UA-6) was obtained in the same manner as UA-3, except that monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 5000) was used.
- the number of curable groups of UA-6 was 1, the number average molecular weight was about 5100, and the viscosity at 25 ° C. was about 3 Pa ⁇ s.
- Non-curable oligomer (C) Non-curable oligomer (1): Bifunctional polypropylene glycol modified with ethylene oxide at the molecular end (number average molecular weight calculated from hydroxyl value: 4000) and trifunctional polypropylene glycol modified at molecular end with ethylene oxide (number average molecular weight calculated from hydroxyl value: 6200) The mixture was mixed at a mass ratio of 1: 1 to obtain a non-curable oligomer (1).
- First composition (1) (A) 20 parts by weight of UA-1, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by mass of the ester M-600A) were uniformly mixed, and then 100 parts by mass of the mixture was mixed with bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF) as the component (D) , IRGACURE (registered trademark) 819), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and antioxidant (manufactured by BASF) , PUR 68) is uniformly dissolved and mixed, and then 100 parts by mass of the mixture is mixed with terminally methylated polypropylene glyco
- Lumpur (number average molecular weight calculated from the hydroxyl value: 1200) homogeneously dissolved 42.9 parts by weight of the mixed, to obtain a first composition (1).
- the viscosity at 25 ° C. of the first composition (1) was 3.2 Pa ⁇ s.
- the concentration of the hydroxyl group in the first composition (1) is 471 ⁇ 10 ⁇ 6 mol / g
- the concentration of the urethane bond is 85 ⁇ 10 ⁇ 6 mol / g
- the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 556 ⁇ 10 ⁇ 6 mol / g
- the SP value was 18.2 (J / cm 3 ) 1/2 .
- the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
- required by calculating the molar concentration of the hydroxyl group contained in (A), (B), (C) component Specifically, in the first composition (1), the phenyl glycidyl ether acrylate of the component (B) has a hydroxyl group, and the concentration of the hydroxyl group is 0.0045 mol / g.
- the components (A), (B), and (C) are mixed in the above blending amounts and calculated as the concentration of the hydroxyl group contained in the components (A), (B), and (C), 471 ⁇ 10 ⁇ 6 mol / g.
- the urethane bond concentration was determined by calculating the molar concentration of the urethane bond contained in the components (A), (B), and (C).
- the components (A) UA-1, UA-5, and UA-6 contain a urethane bond, and the molar concentration thereof is 19 ⁇ 10 ⁇ 6 mol / g, 44 ⁇ 10 ⁇ 6 mol / g, and 22 ⁇ 10 ⁇ 6 mol / g.
- the components (A), (B), and (C) are mixed in the above amounts and calculated as the concentration of urethane bonds contained in the components (A), (B), and (C), 85 ⁇ 10 ⁇ 6 mol / G.
- First composition (2) (A) 20 parts by weight of UA-2, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by weight of the ester M-600A) were uniformly mixed, and then 3 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184) was added to 100 parts by weight of the mixture.
- Phenyl glycidyl ether acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy
- 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF, IRGACURE® 184
- the concentration of hydroxyl groups in the first composition (2) is 398 ⁇ 10 ⁇ 6 mol / g
- the concentration of urethane bonds is 85 ⁇ 10 ⁇ 6 mol / g
- the total of the concentration of hydroxyl groups and the concentration of urethane bonds is 483 ⁇ 10 ⁇ 6 mol / g
- the SP value was 18.2 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
- First composition (3) (A) 25.7 parts by mass of polyisoprene methacrylate (manufactured by Kuraray Co., Ltd., UC203) as component (A), 7.7 parts by mass of dicyclopentenyloxyethyl methacrylate as component (B), 2.6 masses of 2-hydroxypropyl acrylate Part, (C) component 54.1 parts by weight of polybutadiene (Evonik Degussa, Polyoil 110), (D) component 1-hydroxy-cyclohexyl-phenyl-ketone (BASF, IRGACURE (registered trademark) 184) And 0.4 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by LAMBSON, Speed Cure TPO) were uniformly mixed to obtain a first composition (3).
- polyisoprene methacrylate manufactured by Kuraray Co., Ltd., UC203
- component (B) 7.7 parts by mass of dicyclopentenyloxye
- the viscosity at 25 ° C. of the first composition (3) was 2.5 Pa ⁇ s.
- the concentration of the hydroxyl group in the first composition (3) is 220 ⁇ 10 ⁇ 6 mol / g
- the concentration of the urethane bond is 0 mol / g
- the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 220 ⁇ 10 ⁇ 6 mol / g
- SP value, 18.0 (J / cm 3) was 1/2. Since the hydroxyl group does not react during curing, the concentration of the hydroxyl group after curing does not change.
- First composition (4) 40 parts by mass of UA-3 as component (A), 40 parts by mass of 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd., light ester HOB) as component (B), and 20 parts by mass of n-dodecyl methacrylate are uniformly mixed.
- the viscosity at 25 ° C. of the first composition (4) was 3.0 Pa ⁇ s.
- the concentration of hydroxyl groups in the first composition (4) is 1925 ⁇ 10 ⁇ 6 mol / g
- the concentration of urethane bonds is 161 ⁇ 10 ⁇ 6 mol / g
- the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is , 2086 ⁇ 10 -6 mol / g
- SP value, 20.3 (J / cm 3) was 1/2. Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
- First composition (5) 50 parts by mass of UA-4 as component (A) and 50 parts by mass of 4-hydroxybutyl acrylate as component (B) are uniformly mixed, and 100 parts by mass of the mixture is mixed with 1-hydroxy- 3 parts by mass of cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and One part by mass of an antioxidant (manufactured by BASF, PUR 68) was uniformly dissolved.
- cyclohexyl-phenyl-ketone manufactured by BASF, IRGACURE® 184
- 2,5-di-tert-butylhydroquinone polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.
- an antioxidant manufactured by BASF, PUR 68
- the viscosity at 25 ° C. of the first composition (5) was 5.9 Pa ⁇ s.
- the concentration of hydroxyl groups in the first composition (5) is 1850 ⁇ 10 ⁇ 6 mol / g
- the concentration of urethane bonds is 74 ⁇ 10 ⁇ 6 mol / g
- the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is 1924 ⁇ 10 ⁇ 6 mol / g
- the SP value was 19.6 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
- Second composition (1) As a component (F), 55 parts by mass of UA-4 and as a component (G) 45 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4HBA) were uniformly mixed to obtain a mixture.
- a base composition was obtained by uniformly mixing 0.3 parts by mass of an antioxidant and an antioxidant (IRGANOX (registered trademark) 1010, manufactured by BASF). 25 parts by mass of the non-curable oligomer (1) was uniformly dissolved in 75 parts by mass of the base composition to obtain a second composition (1).
- the viscosity at 25 ° C. of the second composition (1) was 60 Pa ⁇ s.
- Example 1 Production of transparent face material (1) with adhesive layer: Using a die coater, the first composition (1) is uniformly applied to the surface of the transparent surface material (1) moving at a constant speed with a thickness of 400 ⁇ m, and UV light is emitted from an LED light source disposed downstream of the die coater. Was irradiated to form a partially cured product layer. A protective film larger than the transparent face material (1) (Puretect (registered trademark) VLH-9, manufactured by Mitsui Chemicals, Inc.) was laminated on the surface of the partially cured product layer.
- Puretect registered trademark
- VLH-9 manufactured by Mitsui Chemicals, Inc.
- Adhesion protected by a protective film by irradiating ultraviolet rays from a high-pressure mercury light source USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 100 mW / cm 2
- a transparent face material (1) with a layer was obtained.
- the irradiation intensity was measured using an illuminance meter (Ushio Electric Co., Ltd., UV intensity meter Unimeter UIT-101).
- the storage shear modulus at 35 ° C. of the partially cured product layer is 700 Pa
- the storage shear modulus at 35 ° C. of the adhesive layer is 5300 Pa.
- Example 2 Production of transparent face material (2) with adhesive layer: Except having used the 1st composition (2) instead of the 1st composition (1), it carried out similarly to Example 1, and obtained the transparent surface material (2) with the adhesion layer protected by the protective film.
- the storage shear modulus at 35 ° C. of the partially cured product layer is 60 Pa
- the storage shear modulus at 35 ° C. of the adhesive layer is 3000 Pa.
- Example 3 Production of transparent face material with adhesive layer (3): A transparent surface material with an adhesive layer (3) protected by a protective film was obtained in the same manner as in Example 1 except that the first composition (5) was used instead of the first composition (1).
- the storage shear modulus at 35 ° C. of the partially cured product layer is 900 Pa
- the storage shear modulus at 35 ° C. of the adhesive layer is 4600 Pa.
- the upper and lower surface plates are brought close to each other by the lifting device in the decompression device, and the polarized light pasted on the object to be bonded (1).
- the plate and the transparent face material (1) with the adhesive layer were pressure-bonded with a pressure of 2 kPa through the adhesive layer and held for 10 seconds.
- the electrostatic chuck was neutralized and the object to be bonded (1) was separated from the upper surface plate, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a simulated display device.
- the transparent film with adhesive layer protected by the protective film (1) to (3) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm.
- One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed.
- the respective results are shown in Table 1 as Examples 1 to 3.
- the peeling speed was 60 mm / min.
- the judgment criteria are as follows: ⁇ : Interfacial peeling (no adhesive layer left on the glass side).
- X Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
- FIG. 14 shows a graph of the total concentration of the hydroxyl groups and urethane bonds in the adhesive layers in Examples 1 to 3 and the bubble disappearance time. It can be seen that there is a correlation between the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer and the bubble disappearance time.
- the unit of hydroxyl group concentration on the horizontal axis in FIG. 13 and the total unit of hydroxyl group concentration and urethane bond concentration on the horizontal axis in FIG. 14 are mol / (g ⁇ 10 6 ).
- Example 4 Production of transparent face material with adhesive layer (4):
- the second composition (1) is applied with a dispenser over the entire circumference at a position of about 25 mm from the outer peripheral edge of the transparent face material (2) so that the width is about 1 mm and the application thickness is about 0.6 mm.
- a semi-cured weir was formed by irradiating ultraviolet rays from the LED light source attached thereto.
- the first composition (1) was supplied to a plurality of locations using a dispenser so that the total mass was 2.5 g. While supplying the first composition (1), there was no breakage such as breakage, and the shape of the semi-cured weir was maintained.
- the transparent surface material (2) is placed flat on the lower surface plate in the decompression device in which a pair of surface plate lifting devices are installed so that the surface coated with the first composition (1) is on the upper surface. did.
- the support surface material with the protective film was held on the upper surface plate in the decompression apparatus with the surface on which the protective film 16 was bonded down. It exhausted until the pressure in a decompression device became about 10,000 Pa, and was hold
- the laminated body was irradiated with ultraviolet rays for 20 seconds from a high-pressure mercury light source (irradiation intensity: 100 mW / cm 2 ) disposed on the support surface material side to cure the semi-cured weir and the uncured adhesive layer to form an adhesive layer. .
- the thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
- the transparent surface material (4) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
- the storage shear modulus at 35 ° C. of the adhesive layer is 7000 Pa.
- Example 5 Production of transparent face material with adhesive layer (5): A transparent surface material (5) with an adhesive layer protected by a protective film was obtained in the same manner as in Example 4 except that the first composition (3) was used instead of the first composition (1).
- the storage shear modulus at 35 ° C. of the adhesive layer is 10500 Pa.
- Example 6 Production of transparent face material (6) with adhesive layer: A laminate was obtained in the same manner as in Example 4 except that the first composition (4) was used instead of the first composition (1).
- the laminated body is irradiated with ultraviolet rays for 10 minutes from a chemical lamp (NEC, FL15BL, irradiation intensity: 2 mW / cm 2 ) disposed on the support surface material side, and the semi-cured weir and the uncured adhesive layer are cured.
- An adhesive layer was formed. The thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
- the transparent surface material (6) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
- the storage shear elastic modulus of the adhesive layer at 35 ° C. is 181000 Pa.
- the transparent film with adhesive layer protected by the protective film (4) to (6) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm.
- One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed.
- the respective results are shown in Table 2 as Examples 4 to 6.
- the peeling speed was 60 mm / min.
- Judgment criteria are as follows. ⁇ : Interfacial peeling (no adhesive layer left on the glass side).
- X Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
- FIG. 15 shows a graph of the concentration of the hydroxyl group in the adhesive layer and the bubble disappearance time in Examples 4 to 6.
- FIG. 16 shows a graph of the total concentration of hydroxyl groups and urethane bonds in the adhesive layers in Examples 4 to 6 and the bubble disappearance time. It can be seen that there is a correlation between the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer and the bubble disappearance time.
- Example 7 Production of pressure-sensitive adhesive sheet with protective film (1): Using a die coater on the surface of a polyethylene terephthalate (PET) film (first substrate) (Purex (registered trademark) manufactured by Teijin Ltd.) whose mold has been released, the first composition (1 ) was continuously applied at a thickness of 500 ⁇ m, and then sandwiched with a PET film (second substrate) (Teijin Purex (registered trademark)) having a surface release property higher than that of the first substrate.
- PET polyethylene terephthalate
- the first composition (1) is completely cured by irradiating ultraviolet rays from a high-pressure mercury light source (USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 1500 mJ / cm 2 ) from the first base material side, and a pressure-sensitive adhesive sheet with a protective film (1) was obtained.
- the storage shear modulus of the pressure-sensitive adhesive sheet at 35 ° C. is 5300 Pa.
- the bubbles remaining at the interface between the object to be bonded and the adhesive layer quickly disappear, A transparent surface material with an adhesive layer in which no defects remain can be produced.
- This transparent surface material with an adhesive layer is useful as a protective plate for display panels, a protective plate for coordinate input devices, a substrate with transparent electrodes for coordinate input devices, and the like.
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Abstract
Provided are: a transparent sheet material coated with a pressure-sensitive adhesive layer, the sheet material, when adhered to an adherend, being capable of making bubbles remaining at the interface between the adherend and the pressure-sensitive adhesive layer rapidly disappear; a display device in which the display panel is protected by the transparent sheet material; processes for producing the transparent sheet material coated with a pressure-sensitive adhesive layer and the display device; and a pressure-sensitive adhesive sheet.
The transparent sheet material (1) coated with a pressure-sensitive adhesive layer comprises a transparent sheet material (10) and, formed on at least one surface of the transparent sheet material (10), a pressure-sensitive adhesive layer (14) constituted of a cured object formed from a curable resin composition, wherein the pressure-sensitive adhesive layer (14) has a concentration of hydroxy groups of 100×10-6 to 600×10-6 mol/g and a concentration of urethane bonds of 0 to 150×10-6 mol/g.
Description
本発明は、粘着層付き透明面材、透明面材によって表示パネルが保護された表示装置およびそれらの製造方法、ならびに粘着シートに関する。
The present invention relates to a transparent surface material with an adhesive layer, a display device in which a display panel is protected by the transparent surface material, a manufacturing method thereof, and an adhesive sheet.
透明面材によって表示パネルが保護された表示装置としては、たとえば、下記のものが知られている。
(1)表示パネルと透明面材とを粘着シートを介して貼合した表示装置(特許文献1、2参照)。
(2)表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように貼合した表示装置(特許文献3~5参照)。 As a display device in which a display panel is protected by a transparent surface material, for example, the following is known.
(1) The display apparatus which bonded the display panel and the transparent surface material through the adhesive sheet (referpatent document 1, 2).
(2) A display device in which a display panel and a transparent surface material with an adhesive layer are bonded so that the adhesive layer is in contact with the display panel (see Patent Documents 3 to 5).
(1)表示パネルと透明面材とを粘着シートを介して貼合した表示装置(特許文献1、2参照)。
(2)表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように貼合した表示装置(特許文献3~5参照)。 As a display device in which a display panel is protected by a transparent surface material, for example, the following is known.
(1) The display apparatus which bonded the display panel and the transparent surface material through the adhesive sheet (refer
(2) A display device in which a display panel and a transparent surface material with an adhesive layer are bonded so that the adhesive layer is in contact with the display panel (see Patent Documents 3 to 5).
(1)の表示装置を製造する際には、表示パネルと粘着シートとの界面、および透明面材と粘着シートとの界面に気泡(空隙)が残存しないように、減圧雰囲気下にて表示パネルと透明面材とを粘着シートを介して貼合した後、これを大気圧雰囲気下に戻す方法がとられる。
また、(2)の表示装置を製造する際には、表示パネルと粘着層との界面に気泡(空隙)が残存しないように、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように貼合した後、これを大気圧雰囲気下に戻す方法がとられる。 When manufacturing the display device of (1), the display panel is used in a reduced-pressure atmosphere so that no bubbles (voids) remain at the interface between the display panel and the adhesive sheet and at the interface between the transparent surface material and the adhesive sheet. And a transparent surface material are pasted together via an adhesive sheet, and then a method of returning it to an atmospheric pressure atmosphere is employed.
When the display device of (2) is manufactured, the display panel and the transparent surface material with the adhesive layer are placed under a reduced pressure atmosphere so that bubbles (voids) do not remain at the interface between the display panel and the adhesive layer. Then, after bonding so that the adhesive layer is in contact with the display panel, a method of returning it to the atmospheric pressure atmosphere is employed.
また、(2)の表示装置を製造する際には、表示パネルと粘着層との界面に気泡(空隙)が残存しないように、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように貼合した後、これを大気圧雰囲気下に戻す方法がとられる。 When manufacturing the display device of (1), the display panel is used in a reduced-pressure atmosphere so that no bubbles (voids) remain at the interface between the display panel and the adhesive sheet and at the interface between the transparent surface material and the adhesive sheet. And a transparent surface material are pasted together via an adhesive sheet, and then a method of returning it to an atmospheric pressure atmosphere is employed.
When the display device of (2) is manufactured, the display panel and the transparent surface material with the adhesive layer are placed under a reduced pressure atmosphere so that bubbles (voids) do not remain at the interface between the display panel and the adhesive layer. Then, after bonding so that the adhesive layer is in contact with the display panel, a method of returning it to the atmospheric pressure atmosphere is employed.
これらの方法によれば、前記界面に気泡が残存していても、減圧雰囲気下の表示装置を大気圧雰囲気下に戻すことによって、気泡内の圧力(すなわち、減圧のままの状態の圧力)と粘着シートや粘着層にかかる圧力(すなわち、大気圧)との差圧によって気泡の体積が減少し、気泡は消滅する。
しかし、従来の粘着シートや粘着層付き透明面材を用いた場合、前記界面に残存した気泡が消滅するのに時間がかかることがあった。前記界面に残存した気泡が消滅するのに時間がかかると、表示装置の生産性が低下する。 According to these methods, even if bubbles remain at the interface, the pressure in the bubbles (that is, the pressure in the reduced pressure state) is reduced by returning the display device in the reduced pressure atmosphere to the atmospheric pressure atmosphere. The volume of the bubbles decreases due to the pressure difference between the pressure applied to the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer (ie, atmospheric pressure), and the bubbles disappear.
However, when a conventional pressure-sensitive adhesive sheet or a transparent surface material with a pressure-sensitive adhesive layer is used, it may take time for the bubbles remaining at the interface to disappear. If it takes time for the bubbles remaining at the interface to disappear, the productivity of the display device is lowered.
しかし、従来の粘着シートや粘着層付き透明面材を用いた場合、前記界面に残存した気泡が消滅するのに時間がかかることがあった。前記界面に残存した気泡が消滅するのに時間がかかると、表示装置の生産性が低下する。 According to these methods, even if bubbles remain at the interface, the pressure in the bubbles (that is, the pressure in the reduced pressure state) is reduced by returning the display device in the reduced pressure atmosphere to the atmospheric pressure atmosphere. The volume of the bubbles decreases due to the pressure difference between the pressure applied to the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer (ie, atmospheric pressure), and the bubbles disappear.
However, when a conventional pressure-sensitive adhesive sheet or a transparent surface material with a pressure-sensitive adhesive layer is used, it may take time for the bubbles remaining at the interface to disappear. If it takes time for the bubbles remaining at the interface to disappear, the productivity of the display device is lowered.
本発明は、被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材;被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材を製造する方法;表示パネルと粘着層との界面への気泡の残存が抑えられた表示装置;表示パネルと粘着層との界面への気泡の残存が抑えられた表示装置を生産性よく製造する方法;および被貼合物と貼合した際に、被貼合物と粘着シートとの界面に残存する気泡が迅速に消滅し得る粘着シートを提供する。
The present invention provides a transparent surface with an adhesive layer in which bubbles remaining at the interface between the object to be bonded and the adhesive layer can quickly disappear when the object to be bonded and the transparent surface material are bonded via the adhesive layer. Material: A transparent surface material with a pressure-sensitive adhesive layer in which bubbles remaining at the interface between the material to be bonded and the pressure-sensitive adhesive layer can quickly disappear when the material to be bonded and the transparent surface material are bonded via the pressure-sensitive adhesive layer. Method for manufacturing; display device in which bubbles remain at the interface between the display panel and the adhesive layer; method for manufacturing a display device in which bubbles remain at the interface between the display panel and the adhesive layer are suppressed with high productivity And providing a pressure-sensitive adhesive sheet in which bubbles remaining at the interface between the material to be bonded and the pressure-sensitive adhesive sheet can rapidly disappear when bonded to the material to be bonded.
本発明者らは、粘着層の特性と、被貼合物と粘着層との界面に残存する気泡の消滅速度との関係について鋭意検討した結果、粘着層中の水酸基の濃度やウレタン結合の濃度が多い場合に、気泡が消滅するのに時間がかかることを見出した。
As a result of intensive studies on the relationship between the characteristics of the adhesive layer and the disappearance rate of bubbles remaining at the interface between the object to be bonded and the adhesive layer, the inventors have determined the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer. It has been found that it takes time for bubbles to disappear when there are many.
本発明の粘着層付き透明面材は、透明面材と、前記透明面材の少なくとも一方の表面に形成された、硬化性樹脂組成物の硬化物からなる粘着層とを有し、前記粘着層中の水酸基の濃度が、100×10-6~600×10-6モル/gであり、前記粘着層中のウレタン結合の濃度が、0~150×10-6モル/gである。
前記粘着層中の水酸基の濃度と前記粘着層中のウレタン結合の濃度との合計は、100×10-6~750×10-6mol/gであることが好ましい。
前記粘着層の溶解度パラメータは、17.5~18.5(J/cm3)1/2であることが好ましい。 The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition, formed on at least one surface of the transparent surface material, and the adhesive layer The concentration of hydroxyl groups therein is 100 × 10 −6 to 600 × 10 −6 mol / g, and the concentration of urethane bonds in the adhesive layer is 0 to 150 × 10 −6 mol / g.
The total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 × 10 −6 to 750 × 10 −6 mol / g.
The solubility parameter of the adhesive layer is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
前記粘着層中の水酸基の濃度と前記粘着層中のウレタン結合の濃度との合計は、100×10-6~750×10-6mol/gであることが好ましい。
前記粘着層の溶解度パラメータは、17.5~18.5(J/cm3)1/2であることが好ましい。 The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition, formed on at least one surface of the transparent surface material, and the adhesive layer The concentration of hydroxyl groups therein is 100 × 10 −6 to 600 × 10 −6 mol / g, and the concentration of urethane bonds in the adhesive layer is 0 to 150 × 10 −6 mol / g.
The total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 × 10 −6 to 750 × 10 −6 mol / g.
The solubility parameter of the adhesive layer is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)とを含み、前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有することが好ましい。前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方は、ウレタン結合を有していてもよい。
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有することが好ましい。前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。
本発明の粘着層付き透明面材は、前記粘着層の表面を覆う、剥離可能な保護フィルムをさらに有することが好ましい。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond, and at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C), It preferably has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
It is preferable that the transparent surface material with an adhesive layer of the present invention further has a peelable protective film that covers the surface of the adhesive layer.
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有することが好ましい。前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。
本発明の粘着層付き透明面材は、前記粘着層の表面を覆う、剥離可能な保護フィルムをさらに有することが好ましい。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond, and at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C), It preferably has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
It is preferable that the transparent surface material with an adhesive layer of the present invention further has a peelable protective film that covers the surface of the adhesive layer.
本発明の粘着層付き透明面材の製造方法は、本発明の粘着層付き透明面材を製造する方法であって、下記工程(α)および下記工程(γ)を有する。
(α)前記透明面材の表面に液状の前記硬化性樹脂組成物を供給し、必要に応じて前記硬化性樹脂組成物を部分的に硬化させて部分硬化物とする工程。
(γ)前記硬化性樹脂組成物または前記部分硬化物を硬化させて、前記粘着層を形成する工程。
本発明の粘着層付き透明面材の製造方法は、下記工程(β)をさらに有することが好ましい。
(β)前記硬化性樹脂組成物または前記部分硬化物の表面を保護フィルムで覆う工程。 The manufacturing method of the transparent surface material with the adhesion layer of this invention is a method of manufacturing the transparent surface material with the adhesion layer of this invention, Comprising: It has the following process ((alpha)) and the following process ((gamma)).
(Α) A step of supplying the liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
(Γ) A step of curing the curable resin composition or the partially cured product to form the adhesive layer.
It is preferable that the manufacturing method of the transparent surface material with the adhesion layer of this invention further has the following process ((beta)).
(Β) A step of covering the surface of the curable resin composition or the partially cured product with a protective film.
(α)前記透明面材の表面に液状の前記硬化性樹脂組成物を供給し、必要に応じて前記硬化性樹脂組成物を部分的に硬化させて部分硬化物とする工程。
(γ)前記硬化性樹脂組成物または前記部分硬化物を硬化させて、前記粘着層を形成する工程。
本発明の粘着層付き透明面材の製造方法は、下記工程(β)をさらに有することが好ましい。
(β)前記硬化性樹脂組成物または前記部分硬化物の表面を保護フィルムで覆う工程。 The manufacturing method of the transparent surface material with the adhesion layer of this invention is a method of manufacturing the transparent surface material with the adhesion layer of this invention, Comprising: It has the following process ((alpha)) and the following process ((gamma)).
(Α) A step of supplying the liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
(Γ) A step of curing the curable resin composition or the partially cured product to form the adhesive layer.
It is preferable that the manufacturing method of the transparent surface material with the adhesion layer of this invention further has the following process ((beta)).
(Β) A step of covering the surface of the curable resin composition or the partially cured product with a protective film.
前記工程(α)が、下記工程(α1)であり、前記工程(β)が、下記工程(β1)であり、前記工程(γ)が、下記工程(γ1)であることが好ましい。
(α1)前記透明面材の表面に液状の前記硬化性樹脂組成物を層状に供給し、前記透明面材の表面に供給された前記硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(β1)前記部分硬化物の層の表面を保護フィルムで覆う工程。
(γ1)前記部分硬化物の層をさらに硬化させて、前記粘着層を形成する工程。 The step (α) is preferably the following step (α1), the step (β) is the following step (β1), and the step (γ) is preferably the following step (γ1).
(Α1) The liquid curable resin composition is supplied in a layer form on the surface of the transparent face material, and the curable resin composition supplied on the surface of the transparent face material is partially cured to be partially cured. Forming a layer.
(Β1) A step of covering the surface of the partially cured product layer with a protective film.
(Γ1) A step of further curing the partially cured product layer to form the adhesive layer.
(α1)前記透明面材の表面に液状の前記硬化性樹脂組成物を層状に供給し、前記透明面材の表面に供給された前記硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(β1)前記部分硬化物の層の表面を保護フィルムで覆う工程。
(γ1)前記部分硬化物の層をさらに硬化させて、前記粘着層を形成する工程。 The step (α) is preferably the following step (α1), the step (β) is the following step (β1), and the step (γ) is preferably the following step (γ1).
(Α1) The liquid curable resin composition is supplied in a layer form on the surface of the transparent face material, and the curable resin composition supplied on the surface of the transparent face material is partially cured to be partially cured. Forming a layer.
(Β1) A step of covering the surface of the partially cured product layer with a protective film.
(Γ1) A step of further curing the partially cured product layer to form the adhesive layer.
また、前記工程(α)が、下記工程(α21)および下記工程(α22)であり、前記工程(β)が、下記工程(β2)であり、前記工程(γ)が、下記工程(γ21)および下記工程(γ22)であることが好ましい。
(α21)前記透明面材の表面の周縁部に枠状の堰を形成する工程。
(α22)前記堰で囲まれた領域に前記硬化性樹脂組成物を供給する工程。
(β2)減圧雰囲気下にて、前記硬化性樹脂組成物の層の上に、保護フィルム付き支持面材を、前記保護フィルムが前記硬化性樹脂組成物の層の表面に接するように重ねて、前記透明面材、前記保護フィルムおよび前記堰で前記硬化性樹脂組成物の層が密封された積層体を得る工程。
(γ21)前記工程(β2)より高い圧力雰囲気下に前記積層体を置いた状態にて、前記硬化性樹脂組成物の層を硬化させて、前記粘着層を形成する工程。
(γ22)前記工程(γ21)の後、前記支持面材を前記保護フィルムから剥離する工程。 The step (α) is the following step (α21) and the following step (α22), the step (β) is the following step (β2), and the step (γ) is the following step (γ21). And the following step (γ22) is preferred.
(Α21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
(Α22) A step of supplying the curable resin composition to a region surrounded by the weir.
(Β2) Under a reduced-pressure atmosphere, the support surface material with a protective film is stacked on the curable resin composition layer so that the protective film is in contact with the surface of the curable resin composition layer, The process of obtaining the laminated body by which the layer of the said curable resin composition was sealed with the said transparent surface material, the said protective film, and the said dam.
(Γ21) A step of forming the adhesive layer by curing the layer of the curable resin composition in a state where the laminate is placed under a higher pressure atmosphere than in the step (β2).
(Γ22) A step of peeling the support surface material from the protective film after the step (γ21).
(α21)前記透明面材の表面の周縁部に枠状の堰を形成する工程。
(α22)前記堰で囲まれた領域に前記硬化性樹脂組成物を供給する工程。
(β2)減圧雰囲気下にて、前記硬化性樹脂組成物の層の上に、保護フィルム付き支持面材を、前記保護フィルムが前記硬化性樹脂組成物の層の表面に接するように重ねて、前記透明面材、前記保護フィルムおよび前記堰で前記硬化性樹脂組成物の層が密封された積層体を得る工程。
(γ21)前記工程(β2)より高い圧力雰囲気下に前記積層体を置いた状態にて、前記硬化性樹脂組成物の層を硬化させて、前記粘着層を形成する工程。
(γ22)前記工程(γ21)の後、前記支持面材を前記保護フィルムから剥離する工程。 The step (α) is the following step (α21) and the following step (α22), the step (β) is the following step (β2), and the step (γ) is the following step (γ21). And the following step (γ22) is preferred.
(Α21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
(Α22) A step of supplying the curable resin composition to a region surrounded by the weir.
(Β2) Under a reduced-pressure atmosphere, the support surface material with a protective film is stacked on the curable resin composition layer so that the protective film is in contact with the surface of the curable resin composition layer, The process of obtaining the laminated body by which the layer of the said curable resin composition was sealed with the said transparent surface material, the said protective film, and the said dam.
(Γ21) A step of forming the adhesive layer by curing the layer of the curable resin composition in a state where the laminate is placed under a higher pressure atmosphere than in the step (β2).
(Γ22) A step of peeling the support surface material from the protective film after the step (γ21).
本発明の表示装置は、表示パネルと、前記粘着層が前記表示パネルに接するように、前記表示パネルに貼合された、本発明の粘着層付き透明面材とを有する。
本発明の表示装置の製造方法は、本発明の表示装置を製造する方法であって、減圧雰囲気下にて、前記表示パネルと前記粘着層付き透明面材とを、前記粘着層が前記表示パネルに接するように重ねて貼合する。 The display apparatus of this invention has a display panel and the transparent surface material with the adhesion layer of this invention bonded by the said display panel so that the said adhesion layer may contact | connect the said display panel.
The display device manufacturing method of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are disposed in a reduced pressure atmosphere, and the adhesive layer is the display panel. Laminate and touch to touch.
本発明の表示装置の製造方法は、本発明の表示装置を製造する方法であって、減圧雰囲気下にて、前記表示パネルと前記粘着層付き透明面材とを、前記粘着層が前記表示パネルに接するように重ねて貼合する。 The display apparatus of this invention has a display panel and the transparent surface material with the adhesion layer of this invention bonded by the said display panel so that the said adhesion layer may contact | connect the said display panel.
The display device manufacturing method of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are disposed in a reduced pressure atmosphere, and the adhesive layer is the display panel. Laminate and touch to touch.
本発明の粘着シートは、硬化性樹脂組成物の硬化物からなる粘着シートであり、前記粘着シート中の水酸基の濃度が、100×10-6~600×10-6モル/gであり、前記粘着シート中のウレタン結合の濃度が、0~150×10-6モル/gである。
前記粘着シート中の水酸基の濃度と前記粘着シート中のウレタン結合の濃度との合計は、100×10-6~750×10-6mol/gであることが好ましい。
前記硬化性樹脂組成物の硬化物の溶解度パラメータは、17.5~18.5(J/cm3)1/2であることが好ましい。 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet made of a cured product of a curable resin composition, and the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet is 100 × 10 −6 to 600 × 10 −6 mol / g, The concentration of urethane bonds in the pressure-sensitive adhesive sheet is 0 to 150 × 10 −6 mol / g.
The total of the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is preferably 100 × 10 −6 to 750 × 10 −6 mol / g.
The solubility parameter of the cured product of the curable resin composition is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
前記粘着シート中の水酸基の濃度と前記粘着シート中のウレタン結合の濃度との合計は、100×10-6~750×10-6mol/gであることが好ましい。
前記硬化性樹脂組成物の硬化物の溶解度パラメータは、17.5~18.5(J/cm3)1/2であることが好ましい。 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet made of a cured product of a curable resin composition, and the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet is 100 × 10 −6 to 600 × 10 −6 mol / g, The concentration of urethane bonds in the pressure-sensitive adhesive sheet is 0 to 150 × 10 −6 mol / g.
The total of the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is preferably 100 × 10 −6 to 750 × 10 −6 mol / g.
The solubility parameter of the cured product of the curable resin composition is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 .
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)とを含み、前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有することが好ましい。前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方は、ウレタン結合を有していてもよい。
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有することが好ましい。前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。
本発明の保護フィルム付き粘着シートは、本発明の粘着シートと、前記粘着シートの少なくとも一方の表面を覆う、剥離可能な保護フィルムとを有する。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond, and at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C), It preferably has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
The pressure-sensitive adhesive sheet with a protective film of the present invention has the pressure-sensitive adhesive sheet of the present invention and a peelable protective film that covers at least one surface of the pressure-sensitive adhesive sheet.
前記硬化性樹脂組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有することが好ましい。前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。
本発明の保護フィルム付き粘着シートは、本発明の粘着シートと、前記粘着シートの少なくとも一方の表面を覆う、剥離可能な保護フィルムとを有する。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and the curing Either or both of the functional oligomer (A) and the low molecular weight polymerizable compound (B) preferably have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond, and at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C), It preferably has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
The pressure-sensitive adhesive sheet with a protective film of the present invention has the pressure-sensitive adhesive sheet of the present invention and a peelable protective film that covers at least one surface of the pressure-sensitive adhesive sheet.
本発明の粘着層付き透明面材によれば、被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。
本発明の粘着層付き透明面材の製造方法によれば、被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材を製造できる。
本発明の表示装置は、表示パネルと粘着層との界面への気泡の残存が抑えられたものとなる。
本発明の表示装置の製造方法によれば、表示パネルと粘着層との界面への気泡の残存が抑えられた表示装置を生産性よく製造できる。
本発明の粘着シートによれば、粘着シートを被貼合物に貼合した際に、被貼合物と粘着シートとの界面に残存する気泡が迅速に消滅し得る。 According to the transparent surface material with an adhesive layer of the present invention, when the object to be bonded and the transparent surface material are bonded via the adhesive layer, bubbles remaining at the interface between the object to be bonded and the adhesive layer are rapidly generated. Can disappear.
According to the method for producing a transparent surface material with an adhesive layer of the present invention, the object to be bonded and the transparent surface material are bonded to each other through the adhesive layer, and remain at the interface between the object to be bonded and the adhesive layer. It is possible to produce a transparent surface material with an adhesive layer in which bubbles can disappear quickly.
In the display device of the present invention, bubbles remain at the interface between the display panel and the adhesive layer.
According to the method for manufacturing a display device of the present invention, it is possible to manufacture a display device in which bubbles are prevented from remaining at the interface between the display panel and the adhesive layer with high productivity.
According to the pressure-sensitive adhesive sheet of the present invention, when the pressure-sensitive adhesive sheet is bonded to the object to be bonded, bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive sheet can quickly disappear.
本発明の粘着層付き透明面材の製造方法によれば、被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材を製造できる。
本発明の表示装置は、表示パネルと粘着層との界面への気泡の残存が抑えられたものとなる。
本発明の表示装置の製造方法によれば、表示パネルと粘着層との界面への気泡の残存が抑えられた表示装置を生産性よく製造できる。
本発明の粘着シートによれば、粘着シートを被貼合物に貼合した際に、被貼合物と粘着シートとの界面に残存する気泡が迅速に消滅し得る。 According to the transparent surface material with an adhesive layer of the present invention, when the object to be bonded and the transparent surface material are bonded via the adhesive layer, bubbles remaining at the interface between the object to be bonded and the adhesive layer are rapidly generated. Can disappear.
According to the method for producing a transparent surface material with an adhesive layer of the present invention, the object to be bonded and the transparent surface material are bonded to each other through the adhesive layer, and remain at the interface between the object to be bonded and the adhesive layer. It is possible to produce a transparent surface material with an adhesive layer in which bubbles can disappear quickly.
In the display device of the present invention, bubbles remain at the interface between the display panel and the adhesive layer.
According to the method for manufacturing a display device of the present invention, it is possible to manufacture a display device in which bubbles are prevented from remaining at the interface between the display panel and the adhesive layer with high productivity.
According to the pressure-sensitive adhesive sheet of the present invention, when the pressure-sensitive adhesive sheet is bonded to the object to be bonded, bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive sheet can quickly disappear.
以下の用語の定義は、本明細書および特許請求の範囲にわたって適用される。
透明面材における「透明」とは、面材と表示パネルの表示面とを粘着層を介して、気泡および/または空隙なく貼合した後に、表示パネルの表示画像の全体または一部が光学的な歪を受けることなく面材を通して視認できる様態を意味する。したがって、表示パネルから面材に入射する光の一部が面材により吸収、反射されたり、または光学的な位相の変化などによって、面材の可視線透過率が低いものであっても、面材を通して光学的な歪なく表示パネルの表示画像を視認することができるのであれば、「透明」であるということができる。
「液状の硬化性樹脂組成物」とは、硬化性樹脂組成物が溶媒を含まない状態で液状であることを意味する。
「硬化性樹脂組成物の硬化物」とは、35℃における貯蔵せん断弾性率が、目標とする粘着層の35℃における貯蔵せん断弾性率になるまで、硬化性樹脂組成物を硬化させたものを意味する。
「部分硬化物」とは、35℃における貯蔵せん断弾性率が、目標とする粘着層の35℃における貯蔵せん断弾性率の1/200~1/5になるまで、硬化性樹脂組成物を硬化させたものを意味する。
「オリゴマー」とは、構成単位(オキシアルキレン単位、ジエン単位等)の繰り返しからなる分子鎖を有する化合物であり、数平均分子量が1,000~100,000のものを意味する。
「低分子量重合性化合物」とは、付加重合性不飽和二重結合を有する、分子量が600以下の化合物を意味する。
「(メタ)アクリレート」とは、アクリレートまたはメタクリレートを意味する。
「粘度」は、25℃においてE型粘度計を用いて測定した値である。
「硬化性オリゴマー(A)の数平均分子量」は、ゲルパーミエーションクロマトグラフィ(以下、GPCと記す。)によって求めた、ポリスチレン換算の数平均分子量である。なお、GPCにおいて、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
「非硬化性オリゴマー(C1)の数平均分子量」は、JIS K 1557-1:2007に準拠して測定した水酸基価A(KOH mg/g)および非硬化性オリゴマー(C)の1分子内の水酸基の数Bから、下式にて算出した値である。
・非硬化性オリゴマー(C)の数平均分子量=56.1×B×1000/A
「粘着層の溶解度パラメータ」(以下、SP値とも記す。)は、Fedorsの計算式を用いて算出した硬化性樹脂組成物の硬化物の溶解度パラメータである。具体的な算出方法については、下記文献を参照する。
山本秀樹著、「SP値基礎・応用と計算方法」、株式会社情報機構。
「粘着層(または堰)の35℃における貯蔵せん断弾性率」は、レオメーター(アントンパール(Anton Paar)社製、モジュラーレオメーター Physica MCR-301)を用い、測定スピンドルと透光性の定板の隙間を粘着層(または堰)の厚さと同一として、その隙間に未硬化の硬化性樹脂組成物を配置し、硬化に必要な熱や光を未硬化の硬化性樹脂組成物に加えながら、測定周波数:1Hzにて、硬化過程の貯蔵せん断弾性率を測定し、粘着層(または堰)を形成する際の硬化条件における計測値を粘着層(または堰)の貯蔵せん断弾性率とする。 The following definitions of terms apply throughout this specification and the claims.
“Transparent” in the transparent surface material means that after the surface material and the display surface of the display panel are bonded to each other through the adhesive layer without bubbles and / or voids, the whole or a part of the display image on the display panel is optical. It means a state that can be visually recognized through the face material without receiving any significant distortion. Therefore, even if part of the light incident on the face material from the display panel is absorbed and reflected by the face material, or the visible material has a low visible ray transmittance due to a change in optical phase, the surface If the display image on the display panel can be viewed through the material without optical distortion, it can be said to be “transparent”.
The “liquid curable resin composition” means that the curable resin composition is in a liquid state without containing a solvent.
The “cured product of the curable resin composition” is a product obtained by curing the curable resin composition until the storage shear modulus at 35 ° C. becomes the target storage shear modulus at 35 ° C. means.
“Partially cured product” means that the curable resin composition is cured until the storage shear modulus at 35 ° C. becomes 1/200 to 1/5 of the storage shear modulus at 35 ° C. of the target adhesive layer. Means something.
“Oligomer” is a compound having a molecular chain composed of repeating structural units (oxyalkylene units, diene units, etc.) and means having a number average molecular weight of 1,000 to 100,000.
The “low molecular weight polymerizable compound” means a compound having an addition polymerizable unsaturated double bond and a molecular weight of 600 or less.
“(Meth) acrylate” means acrylate or methacrylate.
“Viscosity” is a value measured using an E-type viscometer at 25 ° C.
“Number average molecular weight of curable oligomer (A)” is a number average molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter referred to as GPC). In addition, in GPC, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated | required.
“Number average molecular weight of non-curable oligomer (C1)” is a hydroxyl value A (KOH mg / g) measured in accordance with JIS K 1557-1: 2007 and within one molecule of non-curable oligomer (C). It is a value calculated from the number B of hydroxyl groups by the following formula.
-Number average molecular weight of non-curable oligomer (C) = 56.1 x B x 1000 / A
“Adhesion layer solubility parameter” (hereinafter also referred to as SP value) is a solubility parameter of a cured product of the curable resin composition calculated using the Fedors formula. For specific calculation methods, refer to the following documents.
Hideki Yamamoto, “SP Value Basics / Applications and Calculation Methods”, Information Organization Co., Ltd.
“Storage shear modulus of adhesive layer (or weir) at 35 ° C.” is measured using a rheometer (Modular Rheometer Physica MCR-301, manufactured by Anton Paar), and a measuring spindle and a transparent plate. The gap is the same as the thickness of the adhesive layer (or weir), an uncured curable resin composition is placed in the gap, and heat and light necessary for curing are added to the uncured curable resin composition, The storage shear modulus of the curing process is measured at a measurement frequency of 1 Hz, and the measured value in the curing condition when forming the adhesive layer (or weir) is defined as the storage shear modulus of the adhesive layer (or weir).
透明面材における「透明」とは、面材と表示パネルの表示面とを粘着層を介して、気泡および/または空隙なく貼合した後に、表示パネルの表示画像の全体または一部が光学的な歪を受けることなく面材を通して視認できる様態を意味する。したがって、表示パネルから面材に入射する光の一部が面材により吸収、反射されたり、または光学的な位相の変化などによって、面材の可視線透過率が低いものであっても、面材を通して光学的な歪なく表示パネルの表示画像を視認することができるのであれば、「透明」であるということができる。
「液状の硬化性樹脂組成物」とは、硬化性樹脂組成物が溶媒を含まない状態で液状であることを意味する。
「硬化性樹脂組成物の硬化物」とは、35℃における貯蔵せん断弾性率が、目標とする粘着層の35℃における貯蔵せん断弾性率になるまで、硬化性樹脂組成物を硬化させたものを意味する。
「部分硬化物」とは、35℃における貯蔵せん断弾性率が、目標とする粘着層の35℃における貯蔵せん断弾性率の1/200~1/5になるまで、硬化性樹脂組成物を硬化させたものを意味する。
「オリゴマー」とは、構成単位(オキシアルキレン単位、ジエン単位等)の繰り返しからなる分子鎖を有する化合物であり、数平均分子量が1,000~100,000のものを意味する。
「低分子量重合性化合物」とは、付加重合性不飽和二重結合を有する、分子量が600以下の化合物を意味する。
「(メタ)アクリレート」とは、アクリレートまたはメタクリレートを意味する。
「粘度」は、25℃においてE型粘度計を用いて測定した値である。
「硬化性オリゴマー(A)の数平均分子量」は、ゲルパーミエーションクロマトグラフィ(以下、GPCと記す。)によって求めた、ポリスチレン換算の数平均分子量である。なお、GPCにおいて、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
「非硬化性オリゴマー(C1)の数平均分子量」は、JIS K 1557-1:2007に準拠して測定した水酸基価A(KOH mg/g)および非硬化性オリゴマー(C)の1分子内の水酸基の数Bから、下式にて算出した値である。
・非硬化性オリゴマー(C)の数平均分子量=56.1×B×1000/A
「粘着層の溶解度パラメータ」(以下、SP値とも記す。)は、Fedorsの計算式を用いて算出した硬化性樹脂組成物の硬化物の溶解度パラメータである。具体的な算出方法については、下記文献を参照する。
山本秀樹著、「SP値基礎・応用と計算方法」、株式会社情報機構。
「粘着層(または堰)の35℃における貯蔵せん断弾性率」は、レオメーター(アントンパール(Anton Paar)社製、モジュラーレオメーター Physica MCR-301)を用い、測定スピンドルと透光性の定板の隙間を粘着層(または堰)の厚さと同一として、その隙間に未硬化の硬化性樹脂組成物を配置し、硬化に必要な熱や光を未硬化の硬化性樹脂組成物に加えながら、測定周波数:1Hzにて、硬化過程の貯蔵せん断弾性率を測定し、粘着層(または堰)を形成する際の硬化条件における計測値を粘着層(または堰)の貯蔵せん断弾性率とする。 The following definitions of terms apply throughout this specification and the claims.
“Transparent” in the transparent surface material means that after the surface material and the display surface of the display panel are bonded to each other through the adhesive layer without bubbles and / or voids, the whole or a part of the display image on the display panel is optical. It means a state that can be visually recognized through the face material without receiving any significant distortion. Therefore, even if part of the light incident on the face material from the display panel is absorbed and reflected by the face material, or the visible material has a low visible ray transmittance due to a change in optical phase, the surface If the display image on the display panel can be viewed through the material without optical distortion, it can be said to be “transparent”.
The “liquid curable resin composition” means that the curable resin composition is in a liquid state without containing a solvent.
The “cured product of the curable resin composition” is a product obtained by curing the curable resin composition until the storage shear modulus at 35 ° C. becomes the target storage shear modulus at 35 ° C. means.
“Partially cured product” means that the curable resin composition is cured until the storage shear modulus at 35 ° C. becomes 1/200 to 1/5 of the storage shear modulus at 35 ° C. of the target adhesive layer. Means something.
“Oligomer” is a compound having a molecular chain composed of repeating structural units (oxyalkylene units, diene units, etc.) and means having a number average molecular weight of 1,000 to 100,000.
The “low molecular weight polymerizable compound” means a compound having an addition polymerizable unsaturated double bond and a molecular weight of 600 or less.
“(Meth) acrylate” means acrylate or methacrylate.
“Viscosity” is a value measured using an E-type viscometer at 25 ° C.
“Number average molecular weight of curable oligomer (A)” is a number average molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter referred to as GPC). In addition, in GPC, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated | required.
“Number average molecular weight of non-curable oligomer (C1)” is a hydroxyl value A (KOH mg / g) measured in accordance with JIS K 1557-1: 2007 and within one molecule of non-curable oligomer (C). It is a value calculated from the number B of hydroxyl groups by the following formula.
-Number average molecular weight of non-curable oligomer (C) = 56.1 x B x 1000 / A
“Adhesion layer solubility parameter” (hereinafter also referred to as SP value) is a solubility parameter of a cured product of the curable resin composition calculated using the Fedors formula. For specific calculation methods, refer to the following documents.
Hideki Yamamoto, “SP Value Basics / Applications and Calculation Methods”, Information Organization Co., Ltd.
“Storage shear modulus of adhesive layer (or weir) at 35 ° C.” is measured using a rheometer (Modular Rheometer Physica MCR-301, manufactured by Anton Paar), and a measuring spindle and a transparent plate. The gap is the same as the thickness of the adhesive layer (or weir), an uncured curable resin composition is placed in the gap, and heat and light necessary for curing are added to the uncured curable resin composition, The storage shear modulus of the curing process is measured at a measurement frequency of 1 Hz, and the measured value in the curing condition when forming the adhesive layer (or weir) is defined as the storage shear modulus of the adhesive layer (or weir).
<粘着層付き透明面材>
本発明の粘着層付き透明面材は、透明面材と、透明面材の表面に形成された、粘着層形成用硬化性樹脂組成物の硬化物からなる粘着層とを有する。粘着層は、透明面材の少なくとも一方の表面に形成されていてもよく、透明面材の両面に形成されていてもよい。
本発明の粘着層付き透明面材は、必要に応じて、粘着層の周縁に接した状態で粘着層を囲む枠状の堰をさらに有していてもよい。
本発明の粘着層付き透明面材は、必要に応じて、粘着層の表面を覆う、剥離可能な保護フィルムをさらに有していてもよい。 <Transparent surface material with adhesive layer>
The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition for forming an adhesive layer formed on the surface of the transparent surface material. The adhesive layer may be formed on at least one surface of the transparent surface material, or may be formed on both surfaces of the transparent surface material.
The transparent surface material with an adhesive layer of the present invention may further have a frame-like weir surrounding the adhesive layer in contact with the periphery of the adhesive layer, if necessary.
The transparent surface material with an adhesive layer of the present invention may further have a peelable protective film that covers the surface of the adhesive layer, if necessary.
本発明の粘着層付き透明面材は、透明面材と、透明面材の表面に形成された、粘着層形成用硬化性樹脂組成物の硬化物からなる粘着層とを有する。粘着層は、透明面材の少なくとも一方の表面に形成されていてもよく、透明面材の両面に形成されていてもよい。
本発明の粘着層付き透明面材は、必要に応じて、粘着層の周縁に接した状態で粘着層を囲む枠状の堰をさらに有していてもよい。
本発明の粘着層付き透明面材は、必要に応じて、粘着層の表面を覆う、剥離可能な保護フィルムをさらに有していてもよい。 <Transparent surface material with adhesive layer>
The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer made of a cured product of a curable resin composition for forming an adhesive layer formed on the surface of the transparent surface material. The adhesive layer may be formed on at least one surface of the transparent surface material, or may be formed on both surfaces of the transparent surface material.
The transparent surface material with an adhesive layer of the present invention may further have a frame-like weir surrounding the adhesive layer in contact with the periphery of the adhesive layer, if necessary.
The transparent surface material with an adhesive layer of the present invention may further have a peelable protective film that covers the surface of the adhesive layer, if necessary.
(透明面材)
透明面材の形態としては、表示パネルの画像表示面側(視認側)に設けられて表示パネルを保護する保護板;タッチパネル等の座標入力装置の被接触側(視認側)に設けられて座標入力装置を保護する保護板;タッチパネル付き表示装置における、タッチパネル部分を構成する透明電極付き基板等が挙げられる。 (Transparent surface material)
As a form of the transparent surface material, a protective plate provided on the image display surface side (viewing side) of the display panel to protect the display panel; a coordinate provided on the contacted side (viewing side) of a coordinate input device such as a touch panel A protective plate for protecting the input device; for example, a substrate with a transparent electrode constituting a touch panel portion in a display device with a touch panel.
透明面材の形態としては、表示パネルの画像表示面側(視認側)に設けられて表示パネルを保護する保護板;タッチパネル等の座標入力装置の被接触側(視認側)に設けられて座標入力装置を保護する保護板;タッチパネル付き表示装置における、タッチパネル部分を構成する透明電極付き基板等が挙げられる。 (Transparent surface material)
As a form of the transparent surface material, a protective plate provided on the image display surface side (viewing side) of the display panel to protect the display panel; a coordinate provided on the contacted side (viewing side) of a coordinate input device such as a touch panel A protective plate for protecting the input device; for example, a substrate with a transparent electrode constituting a touch panel portion in a display device with a touch panel.
透明面材としては、ガラス板、または透明樹脂板が挙げられる。表示パネルからの出射光や反射光に対して透明性が高い点はもちろん、耐光性、低複屈折性、高い平面精度、耐表面傷付性、高い機械的強度を有する点からも、ガラス板が最も好ましい。後述する製造過程において光硬化性樹脂組成物を硬化させるための光を充分に透過させる点でも、ガラス板が好ましい。
As the transparent face material, a glass plate or a transparent resin plate can be mentioned. The glass plate is not only highly transparent with respect to light emitted from and reflected from the display panel, but also has light resistance, low birefringence, high planar accuracy, surface scratch resistance, and high mechanical strength. Is most preferred. A glass plate is also preferred from the viewpoint of sufficiently transmitting light for curing the photocurable resin composition in the production process described later.
ガラス板の材料としては、ソーダライムガラス等のガラス材料が挙げられ、鉄分がより低く、青みの少ない高透過ガラス(白板ガラスとも呼ばれる)がより好ましい。安全性を高めるために強化ガラスを用いてもよい。特に薄いガラス板を用いる場合には、化学強化を施したガラス板を用いることが好ましい。透明樹脂板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。
As a material of the glass plate, a glass material such as soda lime glass can be mentioned, and a high transmission glass (also referred to as white plate glass) having a lower iron content and less bluishness is more preferable. Tempered glass may be used to increase safety. In particular, when a thin glass plate is used, it is preferable to use a chemically strengthened glass plate. Examples of the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
透明面材には、粘着層との密着性を向上させるために、表面処理を施してもよい。表面処理の方法としては、透明面材の表面をシランカップリング剤で処理する方法、フレームバーナーによる酸化炎によって酸化ケイ素の薄膜を形成する方法等が挙げられる。
The transparent face material may be subjected to a surface treatment in order to improve adhesion with the adhesive layer. Examples of the surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent, a method of forming a silicon oxide thin film by an oxidation flame using a frame burner, and the like.
(粘着層)
粘着層は、液状の粘着層形成用硬化性樹脂組成物を硬化してなる透明樹脂からなる層である。 (Adhesive layer)
The pressure-sensitive adhesive layer is a layer made of a transparent resin obtained by curing a liquid pressure-sensitive adhesive layer-forming curable resin composition.
粘着層は、液状の粘着層形成用硬化性樹脂組成物を硬化してなる透明樹脂からなる層である。 (Adhesive layer)
The pressure-sensitive adhesive layer is a layer made of a transparent resin obtained by curing a liquid pressure-sensitive adhesive layer-forming curable resin composition.
粘着層中の水酸基の濃度は、100×10-6~600×10-6モル/gであり、250×10-6~550×10-6モル/gが好ましく、300×10-6~500×10-6モル/gがより好ましい。粘着層中の水酸基の濃度が100×10-6モル/g以上であれば、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる。
特に、粘着層中の水酸基の濃度が250×10-6モル/g以上であれば、粘着層付き透明面材と被貼合物(表示パネル等)との貼合に失敗した場合において、被貼合物を再利用するために、被貼合物から粘着層付き透明面材を剥がす際に、粘着層が凝集破壊しにくく、粘着層の一部が被貼合物に残存しにくい。被貼合物に粘着層が少しでも残存した場合、被貼合物を再利用できない。
粘着層中の水酸基の濃度が600×10-6モル/g以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。 The concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 to 600 × 10 −6 mol / g, preferably 250 × 10 −6 to 550 × 10 −6 mol / g, and 300 × 10 −6 to 500 × 10 −6 mol / g is more preferable. If the concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material, and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) It becomes good.
In particular, when the concentration of the hydroxyl group in the adhesive layer is 250 × 10 −6 mol / g or more, the bonding between the transparent surface material with the adhesive layer and the object to be bonded (display panel, etc.) fails. In order to reuse the bonded material, when the transparent surface material with the adhesive layer is peeled off from the material to be bonded, the pressure-sensitive adhesive layer is difficult to cohesively break down, and a part of the pressure-sensitive adhesive layer hardly remains in the material to be bonded. When even a little adhesive layer remains on the object to be bonded, the object to be bonded cannot be reused.
If the concentration of the hydroxyl group in the adhesive layer is 600 × 10 −6 mol / g or less, when the transparent surface material with the adhesive layer and the object to be bonded are bonded, the interface between the object to be bonded and the adhesive layer is obtained. The remaining bubbles can disappear quickly.
特に、粘着層中の水酸基の濃度が250×10-6モル/g以上であれば、粘着層付き透明面材と被貼合物(表示パネル等)との貼合に失敗した場合において、被貼合物を再利用するために、被貼合物から粘着層付き透明面材を剥がす際に、粘着層が凝集破壊しにくく、粘着層の一部が被貼合物に残存しにくい。被貼合物に粘着層が少しでも残存した場合、被貼合物を再利用できない。
粘着層中の水酸基の濃度が600×10-6モル/g以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。 The concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 to 600 × 10 −6 mol / g, preferably 250 × 10 −6 to 550 × 10 −6 mol / g, and 300 × 10 −6 to 500 × 10 −6 mol / g is more preferable. If the concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material, and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) It becomes good.
In particular, when the concentration of the hydroxyl group in the adhesive layer is 250 × 10 −6 mol / g or more, the bonding between the transparent surface material with the adhesive layer and the object to be bonded (display panel, etc.) fails. In order to reuse the bonded material, when the transparent surface material with the adhesive layer is peeled off from the material to be bonded, the pressure-sensitive adhesive layer is difficult to cohesively break down, and a part of the pressure-sensitive adhesive layer hardly remains in the material to be bonded. When even a little adhesive layer remains on the object to be bonded, the object to be bonded cannot be reused.
If the concentration of the hydroxyl group in the adhesive layer is 600 × 10 −6 mol / g or less, when the transparent surface material with the adhesive layer and the object to be bonded are bonded, the interface between the object to be bonded and the adhesive layer is obtained. The remaining bubbles can disappear quickly.
粘着層中の水酸基の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中の水酸基の濃度および各原料の配合比から計算によって求める。
硬化性オリゴマー(A)および非硬化性オリゴマー(C)の水酸基の濃度は、オリゴマーを合成する際の原料のモル比から計算によって求める。低分子量重合性化合物(B)の水酸基の濃度は、分子量および官能基数から計算によって求める。
粘着層中の水酸基の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中の水酸基の濃度および各原料の配合比を調整することによって、前記範囲内に調整できる。 The concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. Calculated from the mixing ratio of raw materials.
The density | concentration of the hydroxyl group of a curable oligomer (A) and a non-curable oligomer (C) is calculated | required by calculation from the molar ratio of the raw material at the time of synthesize | combining an oligomer. The hydroxyl group concentration of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
The concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. It can adjust within the said range by adjusting the compounding ratio of a raw material.
硬化性オリゴマー(A)および非硬化性オリゴマー(C)の水酸基の濃度は、オリゴマーを合成する際の原料のモル比から計算によって求める。低分子量重合性化合物(B)の水酸基の濃度は、分子量および官能基数から計算によって求める。
粘着層中の水酸基の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中の水酸基の濃度および各原料の配合比を調整することによって、前記範囲内に調整できる。 The concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. Calculated from the mixing ratio of raw materials.
The density | concentration of the hydroxyl group of a curable oligomer (A) and a non-curable oligomer (C) is calculated | required by calculation from the molar ratio of the raw material at the time of synthesize | combining an oligomer. The hydroxyl group concentration of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
The concentration of the hydroxyl group in the adhesive layer is the concentration of the hydroxyl group in each raw material of the first composition such as the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C), which will be described later. It can adjust within the said range by adjusting the compounding ratio of a raw material.
粘着層中のウレタン結合の濃度は、0~150×10-6モル/gであり、30×10-6~95×10-6モル/gが好ましく、50×10-6~90×10-6モル/gがより好ましい。特に、粘着層中のウレタン結合の濃度が、30×10-6モル/g以上であれば、被貼合物から粘着層付き透明面材を剥がす際に、粘着層が凝集破壊しにくく、粘着層の一部が被貼合物に残存しにくい。粘着層中のウレタン結合の濃度が150×10-6モル/g以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。
なお、粘着層は、気泡の消滅の点からはウレタン結合を有しない方が好ましいが、硬化性オリゴマー(A)の硬化速度を速くしたい場合には、ウレタン結合を有する方が好ましい。 The concentration of urethane bonds in the adhesive layer is 0 to 150 × 10 −6 mol / g, preferably 30 × 10 −6 to 95 × 10 −6 mol / g, and 50 × 10 −6 to 90 × 10 −. 6 mol / g is more preferable. In particular, when the concentration of the urethane bond in the adhesive layer is 30 × 10 −6 mol / g or more, the adhesive layer is less likely to cohesively break down when the transparent surface material with the adhesive layer is peeled off from the object to be bonded. Part of the layer hardly remains on the object to be bonded. When the urethane bond concentration in the adhesive layer is 150 × 10 −6 mol / g or less, the interface between the object to be bonded and the adhesive layer when the transparent surface material with the adhesive layer and the object to be bonded are bonded. The bubbles remaining in the gas can disappear quickly.
The pressure-sensitive adhesive layer preferably has no urethane bond from the viewpoint of the disappearance of bubbles, but preferably has a urethane bond when it is desired to increase the curing rate of the curable oligomer (A).
なお、粘着層は、気泡の消滅の点からはウレタン結合を有しない方が好ましいが、硬化性オリゴマー(A)の硬化速度を速くしたい場合には、ウレタン結合を有する方が好ましい。 The concentration of urethane bonds in the adhesive layer is 0 to 150 × 10 −6 mol / g, preferably 30 × 10 −6 to 95 × 10 −6 mol / g, and 50 × 10 −6 to 90 × 10 −. 6 mol / g is more preferable. In particular, when the concentration of the urethane bond in the adhesive layer is 30 × 10 −6 mol / g or more, the adhesive layer is less likely to cohesively break down when the transparent surface material with the adhesive layer is peeled off from the object to be bonded. Part of the layer hardly remains on the object to be bonded. When the urethane bond concentration in the adhesive layer is 150 × 10 −6 mol / g or less, the interface between the object to be bonded and the adhesive layer when the transparent surface material with the adhesive layer and the object to be bonded are bonded. The bubbles remaining in the gas can disappear quickly.
The pressure-sensitive adhesive layer preferably has no urethane bond from the viewpoint of the disappearance of bubbles, but preferably has a urethane bond when it is desired to increase the curing rate of the curable oligomer (A).
粘着層中のウレタン結合の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中のウレタン結合の濃度および各原料の配合比から計算によって求める。
硬化性オリゴマー(A)および非硬化性オリゴマー(C)のウレタン結合の濃度は、オリゴマーを合成する際の原料のモル比から計算によって求める。低分子量重合性化合物(B)のウレタン結合の濃度は、分子量および官能基数から計算によって求める。
粘着層中のウレタン結合の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中のウレタン結合の濃度および各原料の配合比を調整することによって、前記範囲内に調整できる。
なかでも、硬化性オリゴマー(A1)、低分子量重合性化合物(B1)、非硬化性オリゴマー(C1)の組み合わせである場合は、硬化性オリゴマー(A1)に含まれるウレタン結合の濃度と、各原料の配合比の両方を調整することによって、前記範囲内に調整できる。 The concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it calculates | requires by calculation from the mixture ratio of each raw material.
The concentration of the urethane bond in the curable oligomer (A) and the non-curable oligomer (C) is determined by calculation from the molar ratio of raw materials when the oligomer is synthesized. The concentration of the urethane bond of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
The concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it can adjust within the said range by adjusting the compounding ratio of each raw material.
Especially, when it is a combination of the curable oligomer (A1), the low molecular weight polymerizable compound (B1) and the non-curable oligomer (C1), the concentration of the urethane bond contained in the curable oligomer (A1) and each raw material By adjusting both of the blending ratios, it can be adjusted within the above range.
硬化性オリゴマー(A)および非硬化性オリゴマー(C)のウレタン結合の濃度は、オリゴマーを合成する際の原料のモル比から計算によって求める。低分子量重合性化合物(B)のウレタン結合の濃度は、分子量および官能基数から計算によって求める。
粘着層中のウレタン結合の濃度は、後述する硬化性オリゴマー(A)、低分子量重合性化合物(B)、非硬化性オリゴマー(C)等の第一組成物の各原料中のウレタン結合の濃度および各原料の配合比を調整することによって、前記範囲内に調整できる。
なかでも、硬化性オリゴマー(A1)、低分子量重合性化合物(B1)、非硬化性オリゴマー(C1)の組み合わせである場合は、硬化性オリゴマー(A1)に含まれるウレタン結合の濃度と、各原料の配合比の両方を調整することによって、前記範囲内に調整できる。 The concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it calculates | requires by calculation from the mixture ratio of each raw material.
The concentration of the urethane bond in the curable oligomer (A) and the non-curable oligomer (C) is determined by calculation from the molar ratio of raw materials when the oligomer is synthesized. The concentration of the urethane bond of the low molecular weight polymerizable compound (B) is determined by calculation from the molecular weight and the number of functional groups.
The concentration of urethane bonds in the adhesive layer is the concentration of urethane bonds in each raw material of the first composition such as curable oligomer (A), low molecular weight polymerizable compound (B), and non-curable oligomer (C) described later. And it can adjust within the said range by adjusting the compounding ratio of each raw material.
Especially, when it is a combination of the curable oligomer (A1), the low molecular weight polymerizable compound (B1) and the non-curable oligomer (C1), the concentration of the urethane bond contained in the curable oligomer (A1) and each raw material By adjusting both of the blending ratios, it can be adjusted within the above range.
粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計は、100×10-6~750×10-6mol/gが好ましく、250×10-6~600×10-6モル/gがより好ましい。粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計が100×10-6モル/g以上であれば、硬化性オリゴマー(A)の硬化速度が速く、かつ粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる。
特に、粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計が、250×10-6モル/g以上であれば、被貼合物から粘着層付き透明面材を剥がす際に、粘着層が凝集破壊しにくく、粘着層の一部が被貼合物に残存しにくい。粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計が600×10-6モル/g以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡がさらに迅速に消滅し得る。 The total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 × 10 −6 to 750 × 10 −6 mol / g, and 250 × 10 −6 to 600 × 10 −6 mol. / G is more preferable. When the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 100 × 10 −6 mol / g or more, the curing rate of the curable oligomer (A) is high, and the adhesive layer and the transparent layer are transparent. Adhesion with the face material and adhesion between the adhesive layer and the object to be bonded (display panel or the like) are improved.
In particular, when the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 250 × 10 −6 mol / g or more, the transparent surface material with the adhesive layer is peeled from the object to be bonded. In addition, the adhesive layer is difficult to cohesively break, and a part of the adhesive layer hardly remains on the object to be bonded. When the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 600 × 10 −6 mol / g or less, the transparent surface material with the adhesive layer and the object to be bonded are bonded. In addition, bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more rapidly.
特に、粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計が、250×10-6モル/g以上であれば、被貼合物から粘着層付き透明面材を剥がす際に、粘着層が凝集破壊しにくく、粘着層の一部が被貼合物に残存しにくい。粘着層中の水酸基の濃度と粘着層中のウレタン結合の濃度との合計が600×10-6モル/g以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡がさらに迅速に消滅し得る。 The total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is preferably 100 × 10 −6 to 750 × 10 −6 mol / g, and 250 × 10 −6 to 600 × 10 −6 mol. / G is more preferable. When the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 100 × 10 −6 mol / g or more, the curing rate of the curable oligomer (A) is high, and the adhesive layer and the transparent layer are transparent. Adhesion with the face material and adhesion between the adhesive layer and the object to be bonded (display panel or the like) are improved.
In particular, when the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 250 × 10 −6 mol / g or more, the transparent surface material with the adhesive layer is peeled from the object to be bonded. In addition, the adhesive layer is difficult to cohesively break, and a part of the adhesive layer hardly remains on the object to be bonded. When the sum of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 600 × 10 −6 mol / g or less, the transparent surface material with the adhesive layer and the object to be bonded are bonded. In addition, bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more rapidly.
粘着層(すなわち粘着層形成用硬化性樹脂組成物の硬化物)の溶解度パラメータは、17.5~18.5(J/cm3)1/2が好ましく、18.0~18.45(J/cm3)1/2がより好ましい。溶解度パラメータが17.5(J/cm3)1/2以上であれば、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる。溶解度パラメータが18.5(J/cm3)1/2以下であれば、粘着層付き透明面材と被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡がさらに迅速に消滅し得る。
The solubility parameter of the adhesive layer (that is, the cured product of the curable resin composition for forming the adhesive layer) is preferably 17.5 to 18.5 (J / cm 3 ) 1/2 , and 18.0 to 18.45 (J / Cm 3 ) 1/2 is more preferable. When the solubility parameter is 17.5 (J / cm 3 ) 1/2 or more, the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) are good. It becomes. If the solubility parameter is 18.5 (J / cm 3 ) 1/2 or less, it remains at the interface between the object to be bonded and the adhesive layer when it is bonded to the transparent surface material with the adhesive layer and the object to be bonded. Bubbles can disappear more quickly.
粘着層の35℃における貯蔵せん断弾性率は、1×103~300×103Paが好ましく、1×103~100×103Paがより好ましく、1×103~50×103Paがさらに好ましい。貯蔵せん断弾性率が1×103Pa以上であれば、粘着層の形状を維持できる。また、粘着層の厚さが比較的厚い場合であっても、粘着層全体で厚さを均一に維持でき、粘着層付き透明面材と表示パネルとを貼合する際に、表示パネルと粘着層との界面に気泡が発生しにくい。貯蔵せん断弾性率が300×103Pa以下であれば、表示パネルと貼合させた場合に粘着層が良好な密着性を発揮できる。
また、粘着層を構成する第一組成物の硬化物の分子運動性が比較的高いため、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを貼合した後、これを大気圧雰囲気下に戻した際に、気泡内の圧力(すなわち、減圧雰囲気の減圧のままの状態の圧力)と、粘着層にかかる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧によって気泡の体積が減少しやすくなり、また、体積が減少した気泡内の気体が粘着層に溶解し、吸収されやすい。 The storage shear modulus of the adhesive layer at 35 ° C. is preferably 1 × 10 3 to 300 × 10 3 Pa, more preferably 1 × 10 3 to 100 × 10 3 Pa, and more preferably 1 × 10 3 to 50 × 10 3 Pa. Further preferred. If the storage shear modulus is 1 × 10 3 Pa or more, the shape of the adhesive layer can be maintained. Moreover, even when the thickness of the adhesive layer is relatively large, the thickness can be kept uniform throughout the adhesive layer, and when the transparent surface material with the adhesive layer and the display panel are bonded, Air bubbles are unlikely to occur at the interface with the layer. When the storage shear modulus is 300 × 10 3 Pa or less, the adhesive layer can exhibit good adhesion when bonded to a display panel.
In addition, since the molecular mobility of the cured product of the first composition constituting the adhesive layer is relatively high, after bonding the display panel and the transparent surface material with the adhesive layer under a reduced pressure atmosphere, the atmospheric pressure atmosphere The difference between the pressure inside the bubble (that is, the pressure of the reduced pressure atmosphere in the reduced pressure state) and the pressure applied to the adhesive layer (that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere) The volume of the bubbles is easily reduced by the pressure, and the gas in the bubbles with the reduced volume is easily dissolved and absorbed in the adhesive layer.
また、粘着層を構成する第一組成物の硬化物の分子運動性が比較的高いため、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを貼合した後、これを大気圧雰囲気下に戻した際に、気泡内の圧力(すなわち、減圧雰囲気の減圧のままの状態の圧力)と、粘着層にかかる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧によって気泡の体積が減少しやすくなり、また、体積が減少した気泡内の気体が粘着層に溶解し、吸収されやすい。 The storage shear modulus of the adhesive layer at 35 ° C. is preferably 1 × 10 3 to 300 × 10 3 Pa, more preferably 1 × 10 3 to 100 × 10 3 Pa, and more preferably 1 × 10 3 to 50 × 10 3 Pa. Further preferred. If the storage shear modulus is 1 × 10 3 Pa or more, the shape of the adhesive layer can be maintained. Moreover, even when the thickness of the adhesive layer is relatively large, the thickness can be kept uniform throughout the adhesive layer, and when the transparent surface material with the adhesive layer and the display panel are bonded, Air bubbles are unlikely to occur at the interface with the layer. When the storage shear modulus is 300 × 10 3 Pa or less, the adhesive layer can exhibit good adhesion when bonded to a display panel.
In addition, since the molecular mobility of the cured product of the first composition constituting the adhesive layer is relatively high, after bonding the display panel and the transparent surface material with the adhesive layer under a reduced pressure atmosphere, the atmospheric pressure atmosphere The difference between the pressure inside the bubble (that is, the pressure of the reduced pressure atmosphere in the reduced pressure state) and the pressure applied to the adhesive layer (that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere) The volume of the bubbles is easily reduced by the pressure, and the gas in the bubbles with the reduced volume is easily dissolved and absorbed in the adhesive layer.
粘着層の厚さは、0.03~2mmが好ましく、0.1~0.8mmがより好ましい。粘着層の厚さが0.03mm以上であれば、透明面材側からの外力による衝撃等を粘着層が効果的に緩衝して、表示パネル等を保護できる。また、表示装置の製造方法において、表示パネルと粘着層付き透明面材との間に粘着層の厚さを超えない異物が混入しても、粘着層の厚さが大きく変化することなく、光透過性能への影響が少ない。
粘着層の厚さが2mm以下であれば、粘着層に気泡が残留しにくく、また、表示装置の全体の厚さが不要に厚くならない。粘着層の厚さを調整する方法としては、透明面材の表面に供給される液状の粘着層形成用硬化性樹脂組成物の供給量を調節する方法、堰の厚さを調節する方法等が挙げられる。 The thickness of the adhesive layer is preferably 0.03 to 2 mm, more preferably 0.1 to 0.8 mm. If the thickness of the pressure-sensitive adhesive layer is 0.03 mm or more, the pressure-sensitive adhesive layer effectively buffers an impact or the like due to an external force from the transparent surface material side, and the display panel or the like can be protected. Further, in the manufacturing method of the display device, even if foreign matter not exceeding the thickness of the adhesive layer is mixed between the display panel and the transparent surface material with the adhesive layer, the thickness of the adhesive layer is not significantly changed. Little impact on transmission performance.
If the thickness of the adhesive layer is 2 mm or less, bubbles hardly remain in the adhesive layer, and the entire thickness of the display device does not become unnecessarily thick. As a method for adjusting the thickness of the adhesive layer, there are a method for adjusting the supply amount of the liquid curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material, a method for adjusting the thickness of the weir, etc. Can be mentioned.
粘着層の厚さが2mm以下であれば、粘着層に気泡が残留しにくく、また、表示装置の全体の厚さが不要に厚くならない。粘着層の厚さを調整する方法としては、透明面材の表面に供給される液状の粘着層形成用硬化性樹脂組成物の供給量を調節する方法、堰の厚さを調節する方法等が挙げられる。 The thickness of the adhesive layer is preferably 0.03 to 2 mm, more preferably 0.1 to 0.8 mm. If the thickness of the pressure-sensitive adhesive layer is 0.03 mm or more, the pressure-sensitive adhesive layer effectively buffers an impact or the like due to an external force from the transparent surface material side, and the display panel or the like can be protected. Further, in the manufacturing method of the display device, even if foreign matter not exceeding the thickness of the adhesive layer is mixed between the display panel and the transparent surface material with the adhesive layer, the thickness of the adhesive layer is not significantly changed. Little impact on transmission performance.
If the thickness of the adhesive layer is 2 mm or less, bubbles hardly remain in the adhesive layer, and the entire thickness of the display device does not become unnecessarily thick. As a method for adjusting the thickness of the adhesive layer, there are a method for adjusting the supply amount of the liquid curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material, a method for adjusting the thickness of the weir, etc. Can be mentioned.
(粘着層形成用硬化性樹脂組成物)
粘着層形成用硬化性樹脂組成物は、粘着層を形成し得るものであればよく、特に限定されない。粘着層形成用硬化性樹脂組成物としては、粘着層と透明面材や被貼合物との密着性、被貼合物と粘着層との界面に残存する気泡の消滅の速さの点から、後述する第一組成物が好ましく挙げられる。 (Curable resin composition for forming an adhesive layer)
The adhesive layer forming curable resin composition is not particularly limited as long as it can form an adhesive layer. As the curable resin composition for forming an adhesive layer, from the viewpoint of the adhesiveness between the adhesive layer and the transparent surface material and the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. The 1st composition mentioned later is mentioned preferably.
粘着層形成用硬化性樹脂組成物は、粘着層を形成し得るものであればよく、特に限定されない。粘着層形成用硬化性樹脂組成物としては、粘着層と透明面材や被貼合物との密着性、被貼合物と粘着層との界面に残存する気泡の消滅の速さの点から、後述する第一組成物が好ましく挙げられる。 (Curable resin composition for forming an adhesive layer)
The adhesive layer forming curable resin composition is not particularly limited as long as it can form an adhesive layer. As the curable resin composition for forming an adhesive layer, from the viewpoint of the adhesiveness between the adhesive layer and the transparent surface material and the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. The 1st composition mentioned later is mentioned preferably.
(第一組成物)
第一組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、必要に応じて、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含むものである。
非硬化性オリゴマー(C)を含まない場合は、硬化性オリゴマー(A)および低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有する。硬化性オリゴマー(A)および低分子量重合性化合物(B)のいずれか一方または両方は、ウレタン結合を有していてもよい。
非硬化性オリゴマー(C)を含む場合は、硬化性オリゴマー(A)、低分子量重合性化合物(B)および非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有する。硬化性オリゴマー(A)、低分子量重合性化合物(B)および非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。 (First composition)
The first composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition as necessary. And a non-curable oligomer (C) having no polymerizable unsaturated double bond.
When the non-curable oligomer (C) is not included, either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
When the non-curable oligomer (C) is included, at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
第一組成物は、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、必要に応じて、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含むものである。
非硬化性オリゴマー(C)を含まない場合は、硬化性オリゴマー(A)および低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有する。硬化性オリゴマー(A)および低分子量重合性化合物(B)のいずれか一方または両方は、ウレタン結合を有していてもよい。
非硬化性オリゴマー(C)を含む場合は、硬化性オリゴマー(A)、低分子量重合性化合物(B)および非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有する。硬化性オリゴマー(A)、低分子量重合性化合物(B)および非硬化性オリゴマー(C)のうち少なくとも1つは、ウレタン結合を有していてもよい。 (First composition)
The first composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition as necessary. And a non-curable oligomer (C) having no polymerizable unsaturated double bond.
When the non-curable oligomer (C) is not included, either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) have a hydroxyl group. Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond.
When the non-curable oligomer (C) is included, at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) has a hydroxyl group. At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond.
第一組成物は、光硬化性樹脂組成物であってもよく、熱硬化性樹脂組成物であってもよい。第一組成物としては、低温で硬化でき、かつ硬化速度が速い点から、光重合開始剤(D)がさらに配合された光硬化性樹脂組成物であることが好ましい。また、第一組成物が光硬化性樹脂組成物であれば、硬化には高い温度を必要としないことから、高温による表示パネル等の損傷のおそれも少ない。
第一組成物には、必要に応じて、添加剤が配合されていてもよい。 The first composition may be a photocurable resin composition or a thermosetting resin composition. The first composition is preferably a photocurable resin composition further blended with a photopolymerization initiator (D) because it can be cured at a low temperature and has a high curing rate. In addition, if the first composition is a photocurable resin composition, a high temperature is not required for curing, so that there is little risk of damage to the display panel or the like due to high temperatures.
The first composition may contain an additive as necessary.
第一組成物には、必要に応じて、添加剤が配合されていてもよい。 The first composition may be a photocurable resin composition or a thermosetting resin composition. The first composition is preferably a photocurable resin composition further blended with a photopolymerization initiator (D) because it can be cured at a low temperature and has a high curing rate. In addition, if the first composition is a photocurable resin composition, a high temperature is not required for curing, so that there is little risk of damage to the display panel or the like due to high temperatures.
The first composition may contain an additive as necessary.
硬化性オリゴマー(A)について:
硬化性オリゴマー(A)の付加重合性不飽和二重結合としては、第一組成物の硬化性の点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましく、アクリロイルオキシ基が特に好ましい。
硬化性オリゴマー(A)の粘度は、1~800Pa・sが好ましく、2~600Pa・sがより好ましい。硬化性オリゴマー(A)の粘度が前記範囲内であれば、第一組成物の粘度を後述する範囲に調整しやすい。
硬化性オリゴマー(A)は、1種を単独で用いてもよく、2種以上を併用してもよい。 About curable oligomer (A):
The addition polymerizable unsaturated double bond of the curable oligomer (A) is preferably an acryloyloxy group or a methacryloyloxy group, particularly preferably an acryloyloxy group, from the viewpoint of curability of the first composition.
The viscosity of the curable oligomer (A) is preferably 1 to 800 Pa · s, more preferably 2 to 600 Pa · s. When the viscosity of the curable oligomer (A) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later.
A curable oligomer (A) may be used individually by 1 type, and may use 2 or more types together.
硬化性オリゴマー(A)の付加重合性不飽和二重結合としては、第一組成物の硬化性の点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましく、アクリロイルオキシ基が特に好ましい。
硬化性オリゴマー(A)の粘度は、1~800Pa・sが好ましく、2~600Pa・sがより好ましい。硬化性オリゴマー(A)の粘度が前記範囲内であれば、第一組成物の粘度を後述する範囲に調整しやすい。
硬化性オリゴマー(A)は、1種を単独で用いてもよく、2種以上を併用してもよい。 About curable oligomer (A):
The addition polymerizable unsaturated double bond of the curable oligomer (A) is preferably an acryloyloxy group or a methacryloyloxy group, particularly preferably an acryloyloxy group, from the viewpoint of curability of the first composition.
The viscosity of the curable oligomer (A) is preferably 1 to 800 Pa · s, more preferably 2 to 600 Pa · s. When the viscosity of the curable oligomer (A) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later.
A curable oligomer (A) may be used individually by 1 type, and may use 2 or more types together.
硬化性オリゴマー(A)としては、第一組成物の硬化性および粘着層の機械的特性の点から、数平均分子量が1,000~100,000であり、付加重合性不飽和二重結合の平均数が1.8~4である硬化性オリゴマー(A1)を配合したものが好ましい。
硬化性オリゴマー(A)としては、被貼合物と粘着層との界面に残存する気泡がさらに迅速に消滅し得る点および表示装置の表示ムラを抑える点から、数平均分子量が1,000~20,000であり、付加重合性不飽和二重結合の平均数が0.5~1である硬化性オリゴマー(A2)を配合したものが好ましい。
硬化性オリゴマー(A)としては、硬化性オリゴマー(A1)と硬化性オリゴマー(A2)とを配合したものがより好ましい。 The curable oligomer (A) has a number average molecular weight of 1,000 to 100,000 from the viewpoint of the curability of the first composition and the mechanical properties of the adhesive layer, and is an addition polymerizable unsaturated double bond. A blended curable oligomer (A1) having an average number of 1.8 to 4 is preferred.
The curable oligomer (A) has a number average molecular weight of 1,000 to 1,000 from the viewpoint that bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more quickly and display unevenness of the display device is suppressed. It is preferably 20,000 and blended with a curable oligomer (A2) having an average number of addition polymerizable unsaturated double bonds of 0.5 to 1.
As a curable oligomer (A), what mixed the curable oligomer (A1) and the curable oligomer (A2) is more preferable.
硬化性オリゴマー(A)としては、被貼合物と粘着層との界面に残存する気泡がさらに迅速に消滅し得る点および表示装置の表示ムラを抑える点から、数平均分子量が1,000~20,000であり、付加重合性不飽和二重結合の平均数が0.5~1である硬化性オリゴマー(A2)を配合したものが好ましい。
硬化性オリゴマー(A)としては、硬化性オリゴマー(A1)と硬化性オリゴマー(A2)とを配合したものがより好ましい。 The curable oligomer (A) has a number average molecular weight of 1,000 to 100,000 from the viewpoint of the curability of the first composition and the mechanical properties of the adhesive layer, and is an addition polymerizable unsaturated double bond. A blended curable oligomer (A1) having an average number of 1.8 to 4 is preferred.
The curable oligomer (A) has a number average molecular weight of 1,000 to 1,000 from the viewpoint that bubbles remaining at the interface between the object to be bonded and the adhesive layer can disappear more quickly and display unevenness of the display device is suppressed. It is preferably 20,000 and blended with a curable oligomer (A2) having an average number of addition polymerizable unsaturated double bonds of 0.5 to 1.
As a curable oligomer (A), what mixed the curable oligomer (A1) and the curable oligomer (A2) is more preferable.
硬化性オリゴマー(A1):
硬化性オリゴマー(A1)の数平均分子量は、1,000~100,000であり、10,000~80,000が好ましい。硬化性オリゴマー(A1)の数平均分子量が前記範囲内であれば、第一組成物の粘度を後述する範囲に調整しやすく、表示ムラが抑制された粘着層を形成しやすい。 Curable oligomer (A1):
The number average molecular weight of the curable oligomer (A1) is 1,000 to 100,000, and preferably 10,000 to 80,000. When the number average molecular weight of the curable oligomer (A1) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later, and it is easy to form an adhesive layer in which display unevenness is suppressed.
硬化性オリゴマー(A1)の数平均分子量は、1,000~100,000であり、10,000~80,000が好ましい。硬化性オリゴマー(A1)の数平均分子量が前記範囲内であれば、第一組成物の粘度を後述する範囲に調整しやすく、表示ムラが抑制された粘着層を形成しやすい。 Curable oligomer (A1):
The number average molecular weight of the curable oligomer (A1) is 1,000 to 100,000, and preferably 10,000 to 80,000. When the number average molecular weight of the curable oligomer (A1) is within the above range, it is easy to adjust the viscosity of the first composition to a range described later, and it is easy to form an adhesive layer in which display unevenness is suppressed.
硬化性オリゴマー(A1)の付加重合性不飽和二重結合の平均数は、第一組成物の硬化性および粘着層の機械的特性の点から、1.8~4であり、1.8~3が好ましい。
硬化性オリゴマー(A1)としては、本来であれば、1分子中における付加重合性不飽和二重結合の数が2~4のものが好ましいが、硬化性オリゴマー(A1)を製造する際に、付加重合性不飽和二重結合の数が2未満の副生成物が生じることがある。よって、副生成物も含むものとして、硬化性オリゴマー(A1)の付加重合性不飽和二重結合の平均数は、1.8~4とする。 The average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 in terms of the curability of the first composition and the mechanical properties of the adhesive layer. 3 is preferred.
As the curable oligomer (A1), the number of addition polymerizable unsaturated double bonds in one molecule is preferably 2 to 4, but when the curable oligomer (A1) is produced, By-products with less than 2 addition polymerizable unsaturated double bonds may be formed. Therefore, the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 as including by-products.
硬化性オリゴマー(A1)としては、本来であれば、1分子中における付加重合性不飽和二重結合の数が2~4のものが好ましいが、硬化性オリゴマー(A1)を製造する際に、付加重合性不飽和二重結合の数が2未満の副生成物が生じることがある。よって、副生成物も含むものとして、硬化性オリゴマー(A1)の付加重合性不飽和二重結合の平均数は、1.8~4とする。 The average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 in terms of the curability of the first composition and the mechanical properties of the adhesive layer. 3 is preferred.
As the curable oligomer (A1), the number of addition polymerizable unsaturated double bonds in one molecule is preferably 2 to 4, but when the curable oligomer (A1) is produced, By-products with less than 2 addition polymerizable unsaturated double bonds may be formed. Therefore, the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A1) is 1.8 to 4 as including by-products.
硬化性オリゴマー(A1)としては、柔軟性、耐湿熱性の点から、ポリオキシアルキレン鎖またはポリジエン鎖を有するものが好ましく、ポリオキシアルキレン鎖を有するものがより好ましい。
As the curable oligomer (A1), those having a polyoxyalkylene chain or a polydiene chain are preferred, and those having a polyoxyalkylene chain are more preferred from the viewpoint of flexibility and heat-and-moisture resistance.
ポリジエン鎖を有する硬化性オリゴマー(A1)としては、ポリイソプレン重合体の無水マレイン酸付加物と2-ヒドロキシエチルメタクリレートとのエステル化物(クラレ社製、UC102(数平均分子量:17,000、付加重合性不飽和二重結合の平均数:2)、UC203(数平均分子量:35,000、付加重合性不飽和二重結合の平均数:3)、UC-1(数平均分子量:約25,000))、ポリブタジエン骨格の(メタ)アクリレート系オリゴマー等が挙げられる。
硬化性オリゴマー(A1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 As the curable oligomer (A1) having a polydiene chain, an esterified product of maleic anhydride adduct of polyisoprene polymer and 2-hydroxyethyl methacrylate (Kuraray Co., Ltd., UC102 (number average molecular weight: 17,000, addition polymerization) Average number of polymerizable unsaturated double bonds: 2), UC203 (number average molecular weight: 35,000, average number of addition polymerizable unsaturated double bonds: 3), UC-1 (number average molecular weight: about 25,000) )), (Meth) acrylate oligomers of polybutadiene skeleton and the like.
A curable oligomer (A1) may be used individually by 1 type, and may use 2 or more types together.
硬化性オリゴマー(A1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 As the curable oligomer (A1) having a polydiene chain, an esterified product of maleic anhydride adduct of polyisoprene polymer and 2-hydroxyethyl methacrylate (Kuraray Co., Ltd., UC102 (number average molecular weight: 17,000, addition polymerization) Average number of polymerizable unsaturated double bonds: 2), UC203 (number average molecular weight: 35,000, average number of addition polymerizable unsaturated double bonds: 3), UC-1 (number average molecular weight: about 25,000) )), (Meth) acrylate oligomers of polybutadiene skeleton and the like.
A curable oligomer (A1) may be used individually by 1 type, and may use 2 or more types together.
硬化性オリゴマー(A1)としては、柔軟性の点から、下記する硬化性オリゴマー(A11)または硬化性オリゴマー(A12)が特に好ましい。硬化性オリゴマー(A12)については、後述する。
硬化性オリゴマー(A11):ポリオールとポリイソシアネートとを反応させて末端にイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、下記モノマー(a1)を反応させて得られるウレタンアクリレートオリゴマー。
モノマー(a1):分子量が125~600で、アクリロイルオキシ基を1個以上有し、かつイソシアネート基と反応する基を1個有するモノマー。 As the curable oligomer (A1), the following curable oligomer (A11) or curable oligomer (A12) is particularly preferable from the viewpoint of flexibility. The curable oligomer (A12) will be described later.
Curable oligomer (A11): Urethane acrylate obtained by reacting polyol and polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacting the following monomer (a1) with the isocyanate group of the prepolymer Oligomer.
Monomer (a1): A monomer having a molecular weight of 125 to 600, having one or more acryloyloxy groups and one group that reacts with an isocyanate group.
硬化性オリゴマー(A11):ポリオールとポリイソシアネートとを反応させて末端にイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、下記モノマー(a1)を反応させて得られるウレタンアクリレートオリゴマー。
モノマー(a1):分子量が125~600で、アクリロイルオキシ基を1個以上有し、かつイソシアネート基と反応する基を1個有するモノマー。 As the curable oligomer (A1), the following curable oligomer (A11) or curable oligomer (A12) is particularly preferable from the viewpoint of flexibility. The curable oligomer (A12) will be described later.
Curable oligomer (A11): Urethane acrylate obtained by reacting polyol and polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacting the following monomer (a1) with the isocyanate group of the prepolymer Oligomer.
Monomer (a1): A monomer having a molecular weight of 125 to 600, having one or more acryloyloxy groups and one group that reacts with an isocyanate group.
モノマー(a1)としては、活性水素を有する基(水酸基、アミノ基等)およびアクリロイルオキシ基を有するモノマーが挙げられる。
モノマー(a1)の具体例としては、炭素数2~6のヒドロキシアルキル基を有するヒドロキシアルキルアクリレート(2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート等)等が挙げられる。
モノマー(a1)としては、炭素数2~4のヒドロキシアルキル基を有するヒドロキシアルキルアクリレートが好ましい。
モノマー(a1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the monomer (a1) include monomers having an active hydrogen-containing group (hydroxyl group, amino group, etc.) and an acryloyloxy group.
Specific examples of the monomer (a1) include hydroxyalkyl acrylates having a C 2-6 hydroxyalkyl group (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, etc.) Etc.
The monomer (a1) is preferably a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms.
A monomer (a1) may be used individually by 1 type, and may use 2 or more types together.
モノマー(a1)の具体例としては、炭素数2~6のヒドロキシアルキル基を有するヒドロキシアルキルアクリレート(2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシブチルアクリレート、4-ヒドロキシブチルアクリレート等)等が挙げられる。
モノマー(a1)としては、炭素数2~4のヒドロキシアルキル基を有するヒドロキシアルキルアクリレートが好ましい。
モノマー(a1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the monomer (a1) include monomers having an active hydrogen-containing group (hydroxyl group, amino group, etc.) and an acryloyloxy group.
Specific examples of the monomer (a1) include hydroxyalkyl acrylates having a C 2-6 hydroxyalkyl group (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, etc.) Etc.
The monomer (a1) is preferably a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms.
A monomer (a1) may be used individually by 1 type, and may use 2 or more types together.
ポリオールの具体例としては、ポリオキシアルキレンポリオール(ポリオキシエチレングリコール、ポリオキシプロピレンポリオール等)、ポリエステルポリオール、ポリカーボネートポリオール等が挙げられる。ポリオールとしては、柔軟性の点から、ポリオキシアルキレンポリオールが好ましく、ポリオキシプロピレンポリオールがより好ましい。
また、第一組成物の他の成分との相溶性を高める点から、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンポリオールがさらに好ましい。また、低温域においても柔軟性の高い硬化物が得られやすい点から、オキシエチレン基およびオキシプロピレン基のみからなるポリオキシアルキレン鎖を有するポリオキシアルキレンポリオールが特に好ましい。 Specific examples of the polyol include polyoxyalkylene polyols (polyoxyethylene glycol, polyoxypropylene polyol, etc.), polyester polyols, polycarbonate polyols, and the like. The polyol is preferably a polyoxyalkylene polyol, more preferably a polyoxypropylene polyol, from the viewpoint of flexibility.
Moreover, the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 1st composition. Moreover, the polyoxyalkylene polyol which has a polyoxyalkylene chain which consists only of an oxyethylene group and an oxypropylene group is especially preferable from the point that a highly flexible hardened | cured material is easy to be obtained also in a low temperature range.
また、第一組成物の他の成分との相溶性を高める点から、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンポリオールがさらに好ましい。また、低温域においても柔軟性の高い硬化物が得られやすい点から、オキシエチレン基およびオキシプロピレン基のみからなるポリオキシアルキレン鎖を有するポリオキシアルキレンポリオールが特に好ましい。 Specific examples of the polyol include polyoxyalkylene polyols (polyoxyethylene glycol, polyoxypropylene polyol, etc.), polyester polyols, polycarbonate polyols, and the like. The polyol is preferably a polyoxyalkylene polyol, more preferably a polyoxypropylene polyol, from the viewpoint of flexibility.
Moreover, the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 1st composition. Moreover, the polyoxyalkylene polyol which has a polyoxyalkylene chain which consists only of an oxyethylene group and an oxypropylene group is especially preferable from the point that a highly flexible hardened | cured material is easy to be obtained also in a low temperature range.
ポリオールの数平均分子量は、第一組成物中のウレタン結合の濃度を低くする点から、4,000以上が好ましく、8,000以上がより好ましい。ポリオールの数平均分子量は、第一組成物の粘度を後述の範囲にしやすい点から、45,000以下が好ましく、35,000以下がより好ましい。
ポリオールは、1種を単独で用いてもよく、2種以上を併用してもよい。 The number average molecular weight of the polyol is preferably 4,000 or more, and more preferably 8,000 or more, from the viewpoint of lowering the concentration of urethane bonds in the first composition. The number average molecular weight of the polyol is preferably 45,000 or less, more preferably 35,000 or less, from the viewpoint that the viscosity of the first composition is easily within the range described below.
A polyol may be used individually by 1 type and may use 2 or more types together.
ポリオールは、1種を単独で用いてもよく、2種以上を併用してもよい。 The number average molecular weight of the polyol is preferably 4,000 or more, and more preferably 8,000 or more, from the viewpoint of lowering the concentration of urethane bonds in the first composition. The number average molecular weight of the polyol is preferably 45,000 or less, more preferably 35,000 or less, from the viewpoint that the viscosity of the first composition is easily within the range described below.
A polyol may be used individually by 1 type and may use 2 or more types together.
ポリイソシアネートとしては、脂肪族ジイソシアネート、脂環式ジイソシアネートおよび無黄変性芳香族ジイソシアネートからなる群から選ばれる少なくとも1種のジイソシアネートが好ましい。
脂肪族ポリイソシアネートとしては、ヘキサメチレンジイソシアネート、2,2,4-トリメチル-ヘキサメチレンジイソシアネート、2,4,4-トリメチル-ヘキサメチレンジイソシアネート等が挙げられる。
脂環式ポリイソシアネートとしては、イソホロンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)等が挙げられる。
無黄変性芳香族ジイソシアネートとしては、キシリレンジイソシアネート等が挙げられる。
ポリイソシアネートは、1種を単独で用いてもよく、2種以上を併用してもよい。 The polyisocyanate is preferably at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and non-yellowing aromatic diisocyanates.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
Examples of the non-yellowing aromatic diisocyanate include xylylene diisocyanate.
Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
脂肪族ポリイソシアネートとしては、ヘキサメチレンジイソシアネート、2,2,4-トリメチル-ヘキサメチレンジイソシアネート、2,4,4-トリメチル-ヘキサメチレンジイソシアネート等が挙げられる。
脂環式ポリイソシアネートとしては、イソホロンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)等が挙げられる。
無黄変性芳香族ジイソシアネートとしては、キシリレンジイソシアネート等が挙げられる。
ポリイソシアネートは、1種を単独で用いてもよく、2種以上を併用してもよい。 The polyisocyanate is preferably at least one diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and non-yellowing aromatic diisocyanates.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
Examples of the non-yellowing aromatic diisocyanate include xylylene diisocyanate.
Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
ポリオールと、ポリイソシアネートとの反応において、イソシアネート基のモル数と水酸基のモル数との比(イソシアネート基/水酸基)は、1/1以上1.8/1以下が好ましく、1.05/1以上1.5/1以下がより好ましい。イソシアネート基/水酸基が前記範囲内であれば、第一組成物の粘度を後述する範囲に調整しやすい。
In the reaction between the polyol and the polyisocyanate, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups (isocyanate group / hydroxyl group) is preferably from 1/1 to 1.8 / 1, preferably from 1.05 / 1 or more. 1.5 / 1 or less is more preferable. When the isocyanate group / hydroxyl group is within the above range, it is easy to adjust the viscosity of the first composition to the range described later.
硬化性オリゴマー(A11)の付加重合性不飽和二重結合の平均数を1.8~4に調整する方法としては、硬化性オリゴマー(A11)の製造に用いる原料の配合比を調整する方法が挙げられ、たとえば、下記の(i)(ii)の方法が挙げられる。
(i)付加重合性不飽和二重結合の平均数が1.8~2である硬化性オリゴマー(A11)の場合:
水酸基の平均数が1.8~2であるポリオールと、イソシアネート基の平均数が2であるポリイソシアネートとを反応させて、イソシアネート基の平均数が1.8~2であるプレポリマーを得た後、1分子中に付加重合性不飽和二重結合および水酸基をそれぞれ1個有するモノマー(a11)をイソシアネート基/水酸基のモル数の比が1/1となるように反応させる方法。
(ii)付加重合性不飽和二重結合の平均数が2~4である硬化性オリゴマー(A11)の場合:
水酸基の平均数が2であるポリオールと、イソシアネート基の平均数が2であるポリイソシアネートとを反応させて、イソシアネート基の平均数が2であるプレポリマーを得た後、1分子中に水酸基を1個有し、かつ付加重合性不飽和二重結合を1個以上有するモノマー(a12)をイソシアネート基/水酸基のモル数の比が1/1、付加重合性不飽和二重結合の平均数が2~4となるように反応させる方法。 As a method of adjusting the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A11) to 1.8 to 4, there is a method of adjusting the blending ratio of raw materials used for the production of the curable oligomer (A11). Examples thereof include the following methods (i) and (ii).
(I) In the case of the curable oligomer (A11) having an average number of addition polymerizable unsaturated double bonds of 1.8 to 2:
A polyol having an average number of hydroxyl groups of 1.8 to 2 and a polyisocyanate having an average number of isocyanate groups of 2 were reacted to obtain a prepolymer having an average number of isocyanate groups of 1.8 to 2. Thereafter, the monomer (a11) having one addition polymerizable unsaturated double bond and one hydroxyl group in one molecule is reacted so that the ratio of the number of moles of isocyanate group / hydroxyl group is 1/1.
(Ii) In the case of the curable oligomer (A11) having an average number of addition polymerizable unsaturated double bonds of 2 to 4:
A polyol having an average number of hydroxyl groups of 2 and a polyisocyanate having an average number of isocyanate groups of 2 are reacted to obtain a prepolymer having an average number of isocyanate groups of 2, and then hydroxyl groups in one molecule. The monomer (a12) having one and having at least one addition polymerizable unsaturated double bond has a ratio of the number of moles of isocyanate group / hydroxyl group of 1/1, and the average number of addition polymerizable unsaturated double bonds is A method of reacting to become 2 to 4.
(i)付加重合性不飽和二重結合の平均数が1.8~2である硬化性オリゴマー(A11)の場合:
水酸基の平均数が1.8~2であるポリオールと、イソシアネート基の平均数が2であるポリイソシアネートとを反応させて、イソシアネート基の平均数が1.8~2であるプレポリマーを得た後、1分子中に付加重合性不飽和二重結合および水酸基をそれぞれ1個有するモノマー(a11)をイソシアネート基/水酸基のモル数の比が1/1となるように反応させる方法。
(ii)付加重合性不飽和二重結合の平均数が2~4である硬化性オリゴマー(A11)の場合:
水酸基の平均数が2であるポリオールと、イソシアネート基の平均数が2であるポリイソシアネートとを反応させて、イソシアネート基の平均数が2であるプレポリマーを得た後、1分子中に水酸基を1個有し、かつ付加重合性不飽和二重結合を1個以上有するモノマー(a12)をイソシアネート基/水酸基のモル数の比が1/1、付加重合性不飽和二重結合の平均数が2~4となるように反応させる方法。 As a method of adjusting the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A11) to 1.8 to 4, there is a method of adjusting the blending ratio of raw materials used for the production of the curable oligomer (A11). Examples thereof include the following methods (i) and (ii).
(I) In the case of the curable oligomer (A11) having an average number of addition polymerizable unsaturated double bonds of 1.8 to 2:
A polyol having an average number of hydroxyl groups of 1.8 to 2 and a polyisocyanate having an average number of isocyanate groups of 2 were reacted to obtain a prepolymer having an average number of isocyanate groups of 1.8 to 2. Thereafter, the monomer (a11) having one addition polymerizable unsaturated double bond and one hydroxyl group in one molecule is reacted so that the ratio of the number of moles of isocyanate group / hydroxyl group is 1/1.
(Ii) In the case of the curable oligomer (A11) having an average number of addition polymerizable unsaturated double bonds of 2 to 4:
A polyol having an average number of hydroxyl groups of 2 and a polyisocyanate having an average number of isocyanate groups of 2 are reacted to obtain a prepolymer having an average number of isocyanate groups of 2, and then hydroxyl groups in one molecule. The monomer (a12) having one and having at least one addition polymerizable unsaturated double bond has a ratio of the number of moles of isocyanate group / hydroxyl group of 1/1, and the average number of addition polymerizable unsaturated double bonds is A method of reacting to become 2 to 4.
硬化性オリゴマー(A12)は、下記のオリゴマーである。
硬化性オリゴマー(A12):ポリオールと、イソシアネート基および付加重合性二重結合を1つずつ有する化合物とを反応させて得られるウレタンアクリレートオリゴマー。
ポリオールとしては、硬化性オリゴマー(A11)の製造に用いたものと同様のものを用いることができる。
イソシアネート基および付加重合性二重結合を1つずつ有する化合物としては、たとえば、CH2=C(R)C(O)O-R1-NCOで表わされる化合物(ただし、Rは水素原子またはメチル基であり、R1は炭素数1~6のアルキレン基である。)が特に好ましい。このような化合物としては、カレンズMOI(登録商標)(昭和電工社製、Rがメチル基、R1の炭素数が2)、カレンズAOI(登録商標)(昭和電工社製、Rが水素原子、R1の炭素数が2)等が挙げられる。 The curable oligomer (A12) is the following oligomer.
Curable oligomer (A12): A urethane acrylate oligomer obtained by reacting a polyol with a compound having one isocyanate group and one addition polymerizable double bond.
As a polyol, the thing similar to what was used for manufacture of a curable oligomer (A11) can be used.
Examples of the compound having one isocyanate group and one addition polymerizable double bond include a compound represented by CH 2 ═C (R) C (O) O—R 1 —NCO (where R is a hydrogen atom or methyl And R 1 is an alkylene group having 1 to 6 carbon atoms). Such compounds include Karenz MOI (registered trademark) (manufactured by Showa Denko KK, R is a methyl group, R 1 has 2 carbon atoms), Karenz AOI (registered trademark) (manufactured by Showa Denko KK, R is a hydrogen atom, And R 1 has 2 carbon atoms.
硬化性オリゴマー(A12):ポリオールと、イソシアネート基および付加重合性二重結合を1つずつ有する化合物とを反応させて得られるウレタンアクリレートオリゴマー。
ポリオールとしては、硬化性オリゴマー(A11)の製造に用いたものと同様のものを用いることができる。
イソシアネート基および付加重合性二重結合を1つずつ有する化合物としては、たとえば、CH2=C(R)C(O)O-R1-NCOで表わされる化合物(ただし、Rは水素原子またはメチル基であり、R1は炭素数1~6のアルキレン基である。)が特に好ましい。このような化合物としては、カレンズMOI(登録商標)(昭和電工社製、Rがメチル基、R1の炭素数が2)、カレンズAOI(登録商標)(昭和電工社製、Rが水素原子、R1の炭素数が2)等が挙げられる。 The curable oligomer (A12) is the following oligomer.
Curable oligomer (A12): A urethane acrylate oligomer obtained by reacting a polyol with a compound having one isocyanate group and one addition polymerizable double bond.
As a polyol, the thing similar to what was used for manufacture of a curable oligomer (A11) can be used.
Examples of the compound having one isocyanate group and one addition polymerizable double bond include a compound represented by CH 2 ═C (R) C (O) O—R 1 —NCO (where R is a hydrogen atom or methyl And R 1 is an alkylene group having 1 to 6 carbon atoms). Such compounds include Karenz MOI (registered trademark) (manufactured by Showa Denko KK, R is a methyl group, R 1 has 2 carbon atoms), Karenz AOI (registered trademark) (manufactured by Showa Denko KK, R is a hydrogen atom, And R 1 has 2 carbon atoms.
硬化性オリゴマー(A2):
硬化性オリゴマー(A2)の数平均分子量は、1,000~20,000であり、2,000~10,000が好ましい。硬化性オリゴマー(A2)の数平均分子量が該範囲であれば、第一組成物の粘度を後述する範囲に調整しやすい粘着層を形成しやすい。
硬化性オリゴマー(A)が硬化性オリゴマー(A2)を含むことにより、第一組成物の粘度を後述する範囲に調整しやすい。硬化性オリゴマー(A2)は、実質的に水酸基を有さないため、気泡の消滅性に悪い影響を与えることなく、第一組成物の粘度を調整できる。 Curable oligomer (A2):
The number average molecular weight of the curable oligomer (A2) is 1,000 to 20,000, preferably 2,000 to 10,000. When the number average molecular weight of the curable oligomer (A2) is within this range, it is easy to form an adhesive layer that can easily adjust the viscosity of the first composition to a range described later.
When the curable oligomer (A) contains the curable oligomer (A2), it is easy to adjust the viscosity of the first composition to a range described later. Since the curable oligomer (A2) has substantially no hydroxyl group, the viscosity of the first composition can be adjusted without adversely affecting the disappearance of bubbles.
硬化性オリゴマー(A2)の数平均分子量は、1,000~20,000であり、2,000~10,000が好ましい。硬化性オリゴマー(A2)の数平均分子量が該範囲であれば、第一組成物の粘度を後述する範囲に調整しやすい粘着層を形成しやすい。
硬化性オリゴマー(A)が硬化性オリゴマー(A2)を含むことにより、第一組成物の粘度を後述する範囲に調整しやすい。硬化性オリゴマー(A2)は、実質的に水酸基を有さないため、気泡の消滅性に悪い影響を与えることなく、第一組成物の粘度を調整できる。 Curable oligomer (A2):
The number average molecular weight of the curable oligomer (A2) is 1,000 to 20,000, preferably 2,000 to 10,000. When the number average molecular weight of the curable oligomer (A2) is within this range, it is easy to form an adhesive layer that can easily adjust the viscosity of the first composition to a range described later.
When the curable oligomer (A) contains the curable oligomer (A2), it is easy to adjust the viscosity of the first composition to a range described later. Since the curable oligomer (A2) has substantially no hydroxyl group, the viscosity of the first composition can be adjusted without adversely affecting the disappearance of bubbles.
硬化性オリゴマー(A2)が有する付加重合性不飽和二重結合としては、アクリロイルオキシ基、メタクリロイルオキシ基等が挙げられる。硬化性オリゴマー(A2)の付加重合性不飽和二重結合としては、硬化速度が速い点および透明性の高い粘着層が形成される点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましく、硬化性オリゴマー(A2)と低分子量重合性化合物(B)との付加重合性不飽和二重結合の反応性の差が小さくなり、均質な粘着層が形成される点から、アクリロイルオキシ基が特に好ましい。
Examples of the addition polymerizable unsaturated double bond of the curable oligomer (A2) include an acryloyloxy group and a methacryloyloxy group. The addition polymerizable unsaturated double bond of the curable oligomer (A2) is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of a high curing rate and a highly transparent adhesive layer. An acryloyloxy group is particularly preferred because the difference in the reactivity of the addition polymerizable unsaturated double bond between (A2) and the low molecular weight polymerizable compound (B) is reduced, and a homogeneous adhesive layer is formed.
硬化性オリゴマー(A2)の付加重合性不飽和二重結合の平均数は、第一組成物の硬化性および粘着層の機械的特性の点から、0.5~1であり、0.7~1が好ましい。付加重合性不飽和二重結合の数が1を超えると架橋性を有するオリゴマーとなり、硬化性樹脂組成物の硬化物の貯蔵せん断弾性率が上がりやすくなる。そのため、粘着層と貼合した表示パネルにかかる応力が大きくなり、表示装置の表示ムラが出やすくなる。
また、粘着層の流動性が失われ、貼合の際に粘着層と表示パネルとの界面に生じた気泡が残存しやすい。したがって、付加重合性不飽和二重結合の数が1を超えるものが含まれないように、硬化性オリゴマー(A2)の製造時の原料を選択することが好ましい。
硬化性オリゴマー(A2)は、1種を単独で用いてもよく、2種以上を併用してもよい。 The average number of addition polymerizable unsaturated double bonds of the curable oligomer (A2) is 0.5 to 1 in terms of the curability of the first composition and the mechanical properties of the adhesive layer, and 0.7 to 1 is preferred. When the number of addition polymerizable unsaturated double bonds exceeds 1, it becomes an oligomer having crosslinkability, and the storage shear modulus of the cured product of the curable resin composition tends to increase. Therefore, the stress applied to the display panel bonded to the adhesive layer is increased, and display unevenness of the display device is likely to occur.
Further, the fluidity of the adhesive layer is lost, and bubbles generated at the interface between the adhesive layer and the display panel during bonding are likely to remain. Therefore, it is preferable to select the raw material at the time of manufacturing the curable oligomer (A2) so that the number of addition polymerizable unsaturated double bonds exceeding 1 is not included.
A curable oligomer (A2) may be used individually by 1 type, and may use 2 or more types together.
また、粘着層の流動性が失われ、貼合の際に粘着層と表示パネルとの界面に生じた気泡が残存しやすい。したがって、付加重合性不飽和二重結合の数が1を超えるものが含まれないように、硬化性オリゴマー(A2)の製造時の原料を選択することが好ましい。
硬化性オリゴマー(A2)は、1種を単独で用いてもよく、2種以上を併用してもよい。 The average number of addition polymerizable unsaturated double bonds of the curable oligomer (A2) is 0.5 to 1 in terms of the curability of the first composition and the mechanical properties of the adhesive layer, and 0.7 to 1 is preferred. When the number of addition polymerizable unsaturated double bonds exceeds 1, it becomes an oligomer having crosslinkability, and the storage shear modulus of the cured product of the curable resin composition tends to increase. Therefore, the stress applied to the display panel bonded to the adhesive layer is increased, and display unevenness of the display device is likely to occur.
Further, the fluidity of the adhesive layer is lost, and bubbles generated at the interface between the adhesive layer and the display panel during bonding are likely to remain. Therefore, it is preferable to select the raw material at the time of manufacturing the curable oligomer (A2) so that the number of addition polymerizable unsaturated double bonds exceeding 1 is not included.
A curable oligomer (A2) may be used individually by 1 type, and may use 2 or more types together.
硬化性オリゴマー(A2)としては、柔軟性の点から、下記する硬化性オリゴマー(A21)が好ましい。
硬化性オリゴマー(A21):モノオールとポリイソシアネートとを反応させて片末端のみにイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、モノマー(a1)を反応させて得られるウレタンモノアクリレートオリゴマー。 As the curable oligomer (A2), the following curable oligomer (A21) is preferable from the viewpoint of flexibility.
Curable oligomer (A21): obtained by reacting monool and polyisocyanate to obtain a prepolymer having an isocyanate group only at one end, and then reacting monomer (a1) with the isocyanate group of the prepolymer. Urethane monoacrylate oligomer.
硬化性オリゴマー(A21):モノオールとポリイソシアネートとを反応させて片末端のみにイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、モノマー(a1)を反応させて得られるウレタンモノアクリレートオリゴマー。 As the curable oligomer (A2), the following curable oligomer (A21) is preferable from the viewpoint of flexibility.
Curable oligomer (A21): obtained by reacting monool and polyisocyanate to obtain a prepolymer having an isocyanate group only at one end, and then reacting monomer (a1) with the isocyanate group of the prepolymer. Urethane monoacrylate oligomer.
硬化性オリゴマー(A21)の製造に用いるモノマー(a1)、ポリイソシアネートとしては、硬化性オリゴマー(A11)の製造に用いたものと同様のものが挙げられ、好ましい態様も同様である。モノオールとしては、水酸基数の数を除き、硬化性オリゴマー(A11)の製造に用いたものと同様のものが挙げられ、好ましい態様も同様である。モノオールの好ましい水酸基の数は、1分子中に0.5~1個であり、0.7~1個がより好ましい。
Examples of the monomer (a1) and polyisocyanate used for the production of the curable oligomer (A21) include the same ones as used for the production of the curable oligomer (A11), and preferred embodiments are also the same. Examples of the monool include those similar to those used in the production of the curable oligomer (A11) except for the number of hydroxyl groups, and preferred embodiments are also the same. The preferred number of hydroxyl groups in the monool is 0.5 to 1 in one molecule, more preferably 0.7 to 1.
硬化性オリゴマー(A21)の付加重合性不飽和二重結合の平均数を0.5~1を調整する方法としては、硬化性オリゴマー(A21)の製造に用いる原料の配合比を調整する方法が挙げられ、たとえば、下記の(iii)、(iv)の方法が挙げられる。
(iii)モノオールとジイソシアネートとを、イソシアネート基/水酸基のモル数の比が1/1~2/1となる割合で反応させて、イソシアネート基の平均数が0.5~1であるプレポリマーを得た後、モノマー(a1)をイソシアネート基/イソシアネート基と反応する基とのモル数の比が1/1となるように反応させる方法。
(iv)モノオールと、1分子中にアクリロイルオキシ基とイソシアネート基をそれぞれ1個ずつ有する化合物とを、イソシアネート基/水酸基のモル数の比が1/2~1/1となる割合で反応させて、アクリロイルオキシ基の平均数が0.5~1である化合物を得る方法。 As a method of adjusting the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A21) to 0.5 to 1, there is a method of adjusting the mixing ratio of the raw materials used for the production of the curable oligomer (A21). Examples thereof include the following methods (iii) and (iv).
(Iii) A prepolymer having an average number of isocyanate groups of 0.5 to 1 by reacting monool and diisocyanate at a ratio of isocyanate group / hydroxyl mole number of 1/1 to 2/1. And then the monomer (a1) is reacted so that the ratio of the number of moles of the isocyanate group / the group reacting with the isocyanate group is 1/1.
(Iv) reacting a monool with a compound having one acryloyloxy group and one isocyanate group in one molecule at a ratio in which the molar ratio of isocyanate group / hydroxyl group is 1/2 to 1/1. And obtaining a compound having an average number of acryloyloxy groups of 0.5 to 1.
(iii)モノオールとジイソシアネートとを、イソシアネート基/水酸基のモル数の比が1/1~2/1となる割合で反応させて、イソシアネート基の平均数が0.5~1であるプレポリマーを得た後、モノマー(a1)をイソシアネート基/イソシアネート基と反応する基とのモル数の比が1/1となるように反応させる方法。
(iv)モノオールと、1分子中にアクリロイルオキシ基とイソシアネート基をそれぞれ1個ずつ有する化合物とを、イソシアネート基/水酸基のモル数の比が1/2~1/1となる割合で反応させて、アクリロイルオキシ基の平均数が0.5~1である化合物を得る方法。 As a method of adjusting the average number of addition polymerizable unsaturated double bonds of the curable oligomer (A21) to 0.5 to 1, there is a method of adjusting the mixing ratio of the raw materials used for the production of the curable oligomer (A21). Examples thereof include the following methods (iii) and (iv).
(Iii) A prepolymer having an average number of isocyanate groups of 0.5 to 1 by reacting monool and diisocyanate at a ratio of isocyanate group / hydroxyl mole number of 1/1 to 2/1. And then the monomer (a1) is reacted so that the ratio of the number of moles of the isocyanate group / the group reacting with the isocyanate group is 1/1.
(Iv) reacting a monool with a compound having one acryloyloxy group and one isocyanate group in one molecule at a ratio in which the molar ratio of isocyanate group / hydroxyl group is 1/2 to 1/1. And obtaining a compound having an average number of acryloyloxy groups of 0.5 to 1.
低分子量重合性化合物(B)について:
低分子量重合性化合物(B)の分子量は、600以下であり、140~400が好ましい。低分子量重合性化合物(B)の分子量が小さいほど、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる。低分子量重合性化合物(B)の分子量が140以上であれば、後述の方法によって粘着層付き透明面材や表示装置を製造する際の低分子量重合性化合物(B)の揮発が抑えられる。 About the low molecular weight polymerizable compound (B):
The molecular weight of the low molecular weight polymerizable compound (B) is 600 or less, preferably 140 to 400. The smaller the molecular weight of the low molecular weight polymerizable compound (B), the better the adhesion between the adhesive layer and the transparent surface material, and the adhesion between the adhesive layer and the object to be bonded (display panel, etc.). If the molecular weight of the low molecular weight polymerizable compound (B) is 140 or more, volatilization of the low molecular weight polymerizable compound (B) when the transparent surface material with adhesive layer and the display device are produced by the method described later can be suppressed.
低分子量重合性化合物(B)の分子量は、600以下であり、140~400が好ましい。低分子量重合性化合物(B)の分子量が小さいほど、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる。低分子量重合性化合物(B)の分子量が140以上であれば、後述の方法によって粘着層付き透明面材や表示装置を製造する際の低分子量重合性化合物(B)の揮発が抑えられる。 About the low molecular weight polymerizable compound (B):
The molecular weight of the low molecular weight polymerizable compound (B) is 600 or less, preferably 140 to 400. The smaller the molecular weight of the low molecular weight polymerizable compound (B), the better the adhesion between the adhesive layer and the transparent surface material, and the adhesion between the adhesive layer and the object to be bonded (display panel, etc.). If the molecular weight of the low molecular weight polymerizable compound (B) is 140 or more, volatilization of the low molecular weight polymerizable compound (B) when the transparent surface material with adhesive layer and the display device are produced by the method described later can be suppressed.
低分子量重合性化合物(B)の付加重合性不飽和二重結合の数は、1~3が好ましく、1~2がより好ましい。低分子量重合性化合物(B)としては、付加重合性不飽和二重結合が1個の化合物と、付加重合性不飽和二重結合が2個以上の化合物とを併用したものが好ましい。
The number of addition polymerizable unsaturated double bonds of the low molecular weight polymerizable compound (B) is preferably 1 to 3, more preferably 1 to 2. The low molecular weight polymerizable compound (B) is preferably a combination of a compound having one addition polymerizable unsaturated double bond and a compound having two or more addition polymerizable unsaturated double bonds.
低分子量重合性化合物(B)の付加重合性不飽和二重結合としては、アクリロイルオキシ基、メタクリロイルオキシ基等が挙げられる。低分子量重合性化合物(B)の付加重合性不飽和二重結合としては、硬化速度が速い点および透明性の高い粘着層が形成される点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましく、硬化速度が速い点から、アクリロイルオキシ基が特に好ましい。
低分子量重合性化合物(B)は、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) include an acryloyloxy group and a methacryloyloxy group. The addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of a high curing speed and a highly transparent adhesive layer. An acryloyloxy group is particularly preferred because of its high speed.
A low molecular weight polymeric compound (B) may be used individually by 1 type, and may use 2 or more types together.
低分子量重合性化合物(B)は、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) include an acryloyloxy group and a methacryloyloxy group. The addition polymerizable unsaturated double bond of the low molecular weight polymerizable compound (B) is preferably an acryloyloxy group or a methacryloyloxy group from the viewpoint of a high curing speed and a highly transparent adhesive layer. An acryloyloxy group is particularly preferred because of its high speed.
A low molecular weight polymeric compound (B) may be used individually by 1 type, and may use 2 or more types together.
低分子量重合性化合物(B1):
低分子量重合性化合物(B)としては、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる点、および粘着層中における後述する非硬化性オリゴマー(C1)の分散安定化効果が得られやすい点から、付加重合性不飽和二重結合および炭素原子に結合した水酸基を有する低分子量重合性化合物(B1)を配合したものが好ましい。 Low molecular weight polymerizable compound (B1):
As the low molecular weight polymerizable compound (B), the adhesiveness between the adhesive layer and the transparent surface material, the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.), and the adhesive layer are improved. Incorporating a low molecular weight polymerizable compound (B1) having an addition polymerizable unsaturated double bond and a hydroxyl group bonded to a carbon atom from the viewpoint of easily obtaining a dispersion stabilizing effect of the non-curable oligomer (C1) described later Is preferred.
低分子量重合性化合物(B)としては、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる点、および粘着層中における後述する非硬化性オリゴマー(C1)の分散安定化効果が得られやすい点から、付加重合性不飽和二重結合および炭素原子に結合した水酸基を有する低分子量重合性化合物(B1)を配合したものが好ましい。 Low molecular weight polymerizable compound (B1):
As the low molecular weight polymerizable compound (B), the adhesiveness between the adhesive layer and the transparent surface material, the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.), and the adhesive layer are improved. Incorporating a low molecular weight polymerizable compound (B1) having an addition polymerizable unsaturated double bond and a hydroxyl group bonded to a carbon atom from the viewpoint of easily obtaining a dispersion stabilizing effect of the non-curable oligomer (C1) described later Is preferred.
低分子量重合性化合物(B1)の水酸基の数は、粘着層と透明面材や被貼合物との密着性、被貼合物と粘着層との界面に残存する気泡の消滅の速さの点から、1または2が好ましく、1が特に好ましい。
水酸基を1個有する低分子量重合性化合物(B1)としては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシルメタクリレート、フェニルグリシジルエーテルアクリレート等が挙げられる。
水酸基を2個有する低分子量重合性化合物(B1)としては、グリセリンモノメタクリレート、2,3-ジヒドロキシプロピルアクリレート等が挙げられる。 The number of hydroxyl groups of the low molecular weight polymerizable compound (B1) is determined by the adhesion between the adhesive layer and the transparent surface material or the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. From the viewpoint, 1 or 2 is preferable, and 1 is particularly preferable.
Examples of the low molecular weight polymerizable compound (B1) having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include acrylate, 6-hydroxyhexyl methacrylate, and phenyl glycidyl ether acrylate.
Examples of the low molecular weight polymerizable compound (B1) having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.
水酸基を1個有する低分子量重合性化合物(B1)としては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシルメタクリレート、フェニルグリシジルエーテルアクリレート等が挙げられる。
水酸基を2個有する低分子量重合性化合物(B1)としては、グリセリンモノメタクリレート、2,3-ジヒドロキシプロピルアクリレート等が挙げられる。 The number of hydroxyl groups of the low molecular weight polymerizable compound (B1) is determined by the adhesion between the adhesive layer and the transparent surface material or the object to be bonded, and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. From the viewpoint, 1 or 2 is preferable, and 1 is particularly preferable.
Examples of the low molecular weight polymerizable compound (B1) having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include acrylate, 6-hydroxyhexyl methacrylate, and phenyl glycidyl ether acrylate.
Examples of the low molecular weight polymerizable compound (B1) having two hydroxyl groups include glycerin monomethacrylate and 2,3-dihydroxypropyl acrylate.
低分子量重合性化合物(B1)としては、粘着層と透明面材や被貼合物との密着性の点から、炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレート(2-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート等)またはフェニルグリシジルエーテルアクリレートが好ましく、フェニルグリシジルエーテルアクリレートが特に好ましい。
低分子量重合性化合物(B1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 As the low molecular weight polymerizable compound (B1), hydroxyalkyl methacrylate (2-hydroxypropyl methacrylate) having a hydroxyalkyl group having 3 to 8 carbon atoms from the viewpoint of adhesion between the adhesive layer and the transparent surface material or the object to be bonded. 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc.) or phenyl glycidyl ether acrylate is preferred, and phenyl glycidyl ether acrylate is particularly preferred.
A low molecular weight polymeric compound (B1) may be used individually by 1 type, and may use 2 or more types together.
低分子量重合性化合物(B1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 As the low molecular weight polymerizable compound (B1), hydroxyalkyl methacrylate (2-hydroxypropyl methacrylate) having a hydroxyalkyl group having 3 to 8 carbon atoms from the viewpoint of adhesion between the adhesive layer and the transparent surface material or the object to be bonded. 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc.) or phenyl glycidyl ether acrylate is preferred, and phenyl glycidyl ether acrylate is particularly preferred.
A low molecular weight polymeric compound (B1) may be used individually by 1 type, and may use 2 or more types together.
低分子量重合性化合物(B2):
低分子量重合性化合物(B)は、付加重合性不飽和二重結合を有し、水酸基を有しない低分子量重合性化合物(B2)をさらに配合したものであってもよい。 Low molecular weight polymerizable compound (B2):
The low molecular weight polymerizable compound (B) may further contain a low molecular weight polymerizable compound (B2) having an addition polymerizable unsaturated double bond and no hydroxyl group.
低分子量重合性化合物(B)は、付加重合性不飽和二重結合を有し、水酸基を有しない低分子量重合性化合物(B2)をさらに配合したものであってもよい。 Low molecular weight polymerizable compound (B2):
The low molecular weight polymerizable compound (B) may further contain a low molecular weight polymerizable compound (B2) having an addition polymerizable unsaturated double bond and no hydroxyl group.
非硬化性オリゴマー(C)について:
非硬化性オリゴマー(C)は、第一組成物の硬化時に硬化性オリゴマー(A)、低分子量重合性化合物(B)と反応しないものである。非硬化性オリゴマー(C)は、水酸基を有していてもよく、有していなくてもよい。
非硬化性オリゴマー(C)は、1種を単独で用いてもよく、2種以上を併用してもよい。 About non-curable oligomer (C):
The non-curable oligomer (C) does not react with the curable oligomer (A) and the low molecular weight polymerizable compound (B) when the first composition is cured. The non-curable oligomer (C) may or may not have a hydroxyl group.
A non-curable oligomer (C) may be used individually by 1 type, and may use 2 or more types together.
非硬化性オリゴマー(C)は、第一組成物の硬化時に硬化性オリゴマー(A)、低分子量重合性化合物(B)と反応しないものである。非硬化性オリゴマー(C)は、水酸基を有していてもよく、有していなくてもよい。
非硬化性オリゴマー(C)は、1種を単独で用いてもよく、2種以上を併用してもよい。 About non-curable oligomer (C):
The non-curable oligomer (C) does not react with the curable oligomer (A) and the low molecular weight polymerizable compound (B) when the first composition is cured. The non-curable oligomer (C) may or may not have a hydroxyl group.
A non-curable oligomer (C) may be used individually by 1 type, and may use 2 or more types together.
非硬化性オリゴマー(C)を第一組成物に含ませると、第一組成物の流動性が高まり、粘着層の貯蔵せん断弾性率が低減される。そのため、非硬化性オリゴマー(C)は、減圧雰囲気下で粘着層付き透明面材と被貼合物とを貼合した後に大気圧雰囲気下に戻した際の、被貼合物と粘着層との界面に生じた気泡が消滅するのに必要な時間の短縮に寄与する。
また、非硬化性オリゴマー(C)は、透明面材の表面に第一組成物を塗布し、第一組成物を硬化させる際に透明面材にかかる応力を抑えることができる。
非硬化性オリゴマー(C)は、少量で前記効果を発揮できるが、堰を有する場合、粘着層から堰への非硬化性オリゴマー(C)の拡散が起こるため、粘着層と堰との界面における変形(たとえば、段差)発生による被貼合物との貼合時の気泡の発生または残存の要因となるおそれがある。よって、非硬化性オリゴマー(C)は、後述する量の範囲で用いることが好ましい。 When the non-curable oligomer (C) is included in the first composition, the fluidity of the first composition is increased, and the storage shear modulus of the adhesive layer is reduced. Therefore, the non-curable oligomer (C) is obtained by bonding the transparent surface material with the adhesive layer and the object to be bonded in a reduced pressure atmosphere, and then returning the object to the atmospheric pressure atmosphere. This contributes to shortening the time required for the bubbles generated at the interface of the liquid to disappear.
In addition, the non-curable oligomer (C) can suppress stress applied to the transparent surface material when the first composition is applied to the surface of the transparent surface material and the first composition is cured.
The non-curable oligomer (C) can exert the above-mentioned effect in a small amount, but when it has a weir, the diffusion of the non-curable oligomer (C) from the adhesive layer to the weir occurs, so at the interface between the adhesive layer and the weir. There is a possibility that bubbles may be generated or remain when bonded to an object to be bonded due to deformation (for example, a step). Therefore, it is preferable to use the non-curable oligomer (C) within a range of amounts described later.
また、非硬化性オリゴマー(C)は、透明面材の表面に第一組成物を塗布し、第一組成物を硬化させる際に透明面材にかかる応力を抑えることができる。
非硬化性オリゴマー(C)は、少量で前記効果を発揮できるが、堰を有する場合、粘着層から堰への非硬化性オリゴマー(C)の拡散が起こるため、粘着層と堰との界面における変形(たとえば、段差)発生による被貼合物との貼合時の気泡の発生または残存の要因となるおそれがある。よって、非硬化性オリゴマー(C)は、後述する量の範囲で用いることが好ましい。 When the non-curable oligomer (C) is included in the first composition, the fluidity of the first composition is increased, and the storage shear modulus of the adhesive layer is reduced. Therefore, the non-curable oligomer (C) is obtained by bonding the transparent surface material with the adhesive layer and the object to be bonded in a reduced pressure atmosphere, and then returning the object to the atmospheric pressure atmosphere. This contributes to shortening the time required for the bubbles generated at the interface of the liquid to disappear.
In addition, the non-curable oligomer (C) can suppress stress applied to the transparent surface material when the first composition is applied to the surface of the transparent surface material and the first composition is cured.
The non-curable oligomer (C) can exert the above-mentioned effect in a small amount, but when it has a weir, the diffusion of the non-curable oligomer (C) from the adhesive layer to the weir occurs, so at the interface between the adhesive layer and the weir. There is a possibility that bubbles may be generated or remain when bonded to an object to be bonded due to deformation (for example, a step). Therefore, it is preferable to use the non-curable oligomer (C) within a range of amounts described later.
非硬化性オリゴマー(C1):
非硬化性オリゴマー(C)としては、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる点から、非硬化性オリゴマー(C1)を配合したものが好ましい。 Non-curable oligomer (C1):
The non-curable oligomer (C) is a non-curable oligomer (from the point that the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) are good. What mix | blended C1) is preferable.
非硬化性オリゴマー(C)としては、粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好となる点から、非硬化性オリゴマー(C1)を配合したものが好ましい。 Non-curable oligomer (C1):
The non-curable oligomer (C) is a non-curable oligomer (from the point that the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded (display panel, etc.) are good. What mix | blended C1) is preferable.
非硬化性オリゴマー(C1)の水酸基の平均数は、相溶性、被貼合物と粘着層との界面に残存する気泡の消滅の速さの点から、0.8~3が好ましく、1.8~2.3個がより好ましい。
The average number of hydroxyl groups in the non-curable oligomer (C1) is preferably 0.8 to 3 in terms of compatibility and the speed of disappearance of bubbles remaining at the interface between the object to be bonded and the adhesive layer. More preferably, 8 to 2.3.
非硬化性オリゴマー(C1)の水酸基1個当たりの数平均分子量は、400~8,000が好ましく、600~5,000がより好ましい。水酸基1個当たりの数平均分子量が400以上であれば、非硬化性オリゴマー(C1)の極性が高くなりすぎず、硬化性オリゴマー(A)、低分子量重合性化合物(B)および他の非硬化性オリゴマー(C)との良好な相溶性が得られやすい。
水酸基1個当たりの数平均分子量が8,000以下であれば、低分子量重合性化合物(B1)に由来する水酸基と、非硬化性オリゴマー(C1)の水酸基との間の相互作用によって、硬化後の粘着層中における非硬化性オリゴマー(C1)の分散安定化効果が得られやすい。かかる相互作用には、水素結合が関与すると推測される。
非硬化性オリゴマー(C1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 The number average molecular weight per hydroxyl group of the non-curable oligomer (C1) is preferably 400 to 8,000, more preferably 600 to 5,000. If the number average molecular weight per hydroxyl group is 400 or more, the polarity of the non-curable oligomer (C1) does not become too high, and the curable oligomer (A), the low molecular weight polymerizable compound (B) and other non-cured compounds. Good compatibility with the functional oligomer (C) is easily obtained.
If the number average molecular weight per hydroxyl group is not more than 8,000, after curing due to the interaction between the hydroxyl group derived from the low molecular weight polymerizable compound (B1) and the hydroxyl group of the non-curable oligomer (C1) It is easy to obtain the effect of stabilizing the dispersion of the non-curable oligomer (C1) in the adhesive layer. Such an interaction is presumed to involve hydrogen bonding.
A non-curable oligomer (C1) may be used individually by 1 type, and may use 2 or more types together.
水酸基1個当たりの数平均分子量が8,000以下であれば、低分子量重合性化合物(B1)に由来する水酸基と、非硬化性オリゴマー(C1)の水酸基との間の相互作用によって、硬化後の粘着層中における非硬化性オリゴマー(C1)の分散安定化効果が得られやすい。かかる相互作用には、水素結合が関与すると推測される。
非硬化性オリゴマー(C1)は、1種を単独で用いてもよく、2種以上を併用してもよい。 The number average molecular weight per hydroxyl group of the non-curable oligomer (C1) is preferably 400 to 8,000, more preferably 600 to 5,000. If the number average molecular weight per hydroxyl group is 400 or more, the polarity of the non-curable oligomer (C1) does not become too high, and the curable oligomer (A), the low molecular weight polymerizable compound (B) and other non-cured compounds. Good compatibility with the functional oligomer (C) is easily obtained.
If the number average molecular weight per hydroxyl group is not more than 8,000, after curing due to the interaction between the hydroxyl group derived from the low molecular weight polymerizable compound (B1) and the hydroxyl group of the non-curable oligomer (C1) It is easy to obtain the effect of stabilizing the dispersion of the non-curable oligomer (C1) in the adhesive layer. Such an interaction is presumed to involve hydrogen bonding.
A non-curable oligomer (C1) may be used individually by 1 type, and may use 2 or more types together.
非硬化性オリゴマー(C1)としては、高分子量のポリオール等が挙げられる。非硬化性オリゴマー(C1)としては、柔軟性、相溶性の点から、ポリオキシアルキレンポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオールが好ましい。
また、硬化性オリゴマー(A)が、ポリオキシアルキレンポリオールを原料として用いるウレタンアクリレートである場合、非硬化性オリゴマー(C1)としては、相溶性がより良くなる点から、ポリオキシアルキレンポリオールがより好ましい。
ポリオキシアルキレンポリオールとしては、ポリオキシエチレングリコール、ポリオキシプロピレンジオール、ポリオキシプロピレントリオール、ポリオキシテトラメチレングリコール等のポリオキシアルキレンジオールが挙げられる。 Examples of the non-curable oligomer (C1) include a high molecular weight polyol. The non-curable oligomer (C1) is preferably a polyoxyalkylene polyol, a polyester polyol, a polycarbonate polyol, or a polybutadiene polyol from the viewpoint of flexibility and compatibility.
When the curable oligomer (A) is a urethane acrylate using a polyoxyalkylene polyol as a raw material, the non-curable oligomer (C1) is more preferably a polyoxyalkylene polyol from the viewpoint of better compatibility. .
Examples of the polyoxyalkylene polyol include polyoxyalkylene diols such as polyoxyethylene glycol, polyoxypropylene diol, polyoxypropylene triol, and polyoxytetramethylene glycol.
また、硬化性オリゴマー(A)が、ポリオキシアルキレンポリオールを原料として用いるウレタンアクリレートである場合、非硬化性オリゴマー(C1)としては、相溶性がより良くなる点から、ポリオキシアルキレンポリオールがより好ましい。
ポリオキシアルキレンポリオールとしては、ポリオキシエチレングリコール、ポリオキシプロピレンジオール、ポリオキシプロピレントリオール、ポリオキシテトラメチレングリコール等のポリオキシアルキレンジオールが挙げられる。 Examples of the non-curable oligomer (C1) include a high molecular weight polyol. The non-curable oligomer (C1) is preferably a polyoxyalkylene polyol, a polyester polyol, a polycarbonate polyol, or a polybutadiene polyol from the viewpoint of flexibility and compatibility.
When the curable oligomer (A) is a urethane acrylate using a polyoxyalkylene polyol as a raw material, the non-curable oligomer (C1) is more preferably a polyoxyalkylene polyol from the viewpoint of better compatibility. .
Examples of the polyoxyalkylene polyol include polyoxyalkylene diols such as polyoxyethylene glycol, polyoxypropylene diol, polyoxypropylene triol, and polyoxytetramethylene glycol.
非硬化性オリゴマー(C1)としては、粘着層の貯蔵せん断弾性率が低くなりやすい点から、ポリオキシアルキレンポリオールが好ましく、ポリオキシプロピレンポリオールが特に好ましい。また、非硬化性オリゴマー(C1)としては、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンポリオールを用いてもよい。
As the non-curable oligomer (C1), a polyoxyalkylene polyol is preferable, and a polyoxypropylene polyol is particularly preferable because the storage shear modulus of the adhesive layer tends to be low. Further, as the non-curable oligomer (C1), a polyoxyalkylene polyol having an oxypropylene group and an oxyethylene group may be used.
非硬化性オリゴマー(C2):
非硬化性オリゴマー(C)は、水酸基を有しない非硬化性オリゴマー(C2)をさらに配合したものであってもよい。 Non-curable oligomer (C2):
The non-curable oligomer (C) may be further blended with a non-curable oligomer (C2) having no hydroxyl group.
非硬化性オリゴマー(C)は、水酸基を有しない非硬化性オリゴマー(C2)をさらに配合したものであってもよい。 Non-curable oligomer (C2):
The non-curable oligomer (C) may be further blended with a non-curable oligomer (C2) having no hydroxyl group.
非硬化性オリゴマー(C2)の数平均分子量は、1,000~8,000が好ましい。非硬化性オリゴマー(C2)の数平均分子量が1,000以上あれば非硬化性オリゴマー(C2)がブリードアウトしにくい。非硬化性オリゴマー(C2)の数平均分子量が8,000以下であれば第一組成物の粘度を後述の範囲に調整しやすくなる。
The number average molecular weight of the non-curable oligomer (C2) is preferably 1,000 to 8,000. If the number average molecular weight of the non-curable oligomer (C2) is 1,000 or more, the non-curable oligomer (C2) is difficult to bleed out. If the number average molecular weight of the non-curable oligomer (C2) is 8,000 or less, it becomes easy to adjust the viscosity of the first composition to a range described later.
非硬化性オリゴマー(C2)としては、非硬化性オリゴマー(C1)の水酸基がアクリロイル基と反応性を有さない基で置換された化合物、高分子量のポリジエン等が挙げられる。ポリジエンとしては、ポリブタジエン、ポリイソプレン、ポリブタジエンの水添加物、ポリブテン等が挙げられる。非硬化性オリゴマー(C1)の水酸基がアクリロイル基と反応性を有さない基で置換された化合物としては、ポリオキシアルキレンポリオールのアルコキシ化物、モノカルボン酸化物、ハロゲン化アセチル化物、エステル化物等が挙げられる。
Examples of the non-curable oligomer (C2) include a compound in which the hydroxyl group of the non-curable oligomer (C1) is substituted with a group having no reactivity with the acryloyl group, and a high molecular weight polydiene. Examples of the polydiene include polybutadiene, polyisoprene, a water additive of polybutadiene, and polybutene. Examples of the compound in which the hydroxyl group of the non-curable oligomer (C1) is substituted with a group that is not reactive with the acryloyl group include polyoxyalkylene polyol alkoxylated products, monocarboxylic oxides, halogenated acetylated products, and esterified products. Can be mentioned.
硬化性オリゴマー(A)と非硬化性オリゴマー(C)との組み合わせについて:
硬化性オリゴマー(A)および非硬化性オリゴマー(C)は、硬化前の第一組成物の混合状態を安定にし、かつ粘着層から非硬化性オリゴマー(C)が分離することを抑える点から、同一構造または類似構造の分子鎖を有することが好ましい。 About the combination of the curable oligomer (A) and the non-curable oligomer (C):
From the point that the curable oligomer (A) and the non-curable oligomer (C) stabilize the mixed state of the first composition before curing and suppress the separation of the non-curable oligomer (C) from the adhesive layer. It is preferable to have molecular chains having the same structure or a similar structure.
硬化性オリゴマー(A)および非硬化性オリゴマー(C)は、硬化前の第一組成物の混合状態を安定にし、かつ粘着層から非硬化性オリゴマー(C)が分離することを抑える点から、同一構造または類似構造の分子鎖を有することが好ましい。 About the combination of the curable oligomer (A) and the non-curable oligomer (C):
From the point that the curable oligomer (A) and the non-curable oligomer (C) stabilize the mixed state of the first composition before curing and suppress the separation of the non-curable oligomer (C) from the adhesive layer. It is preferable to have molecular chains having the same structure or a similar structure.
具体的には、硬化性オリゴマー(A)の原料として、水酸基を有する化合物(以下、水酸基含有化合物と記す。)を用いるとともに、同じ水酸基含有化合物を非硬化性オリゴマー(C)として用いることが好ましい。
第一組成物においては、硬化性オリゴマー(A)が、ポリオキシアルキレンポリオールおよびポリイソシアネートを原料に用いて合成されたウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、ポリオキシアルキレンポリオールであることが、相溶性の点で好ましい。 Specifically, it is preferable to use a compound having a hydroxyl group (hereinafter referred to as a hydroxyl group-containing compound) as a raw material for the curable oligomer (A) and to use the same hydroxyl group-containing compound as the non-curable oligomer (C). .
In the first composition, the curable oligomer (A) is a urethane acrylate oligomer synthesized using polyoxyalkylene polyol and polyisocyanate as raw materials, and the non-curable oligomer (C) is a polyoxyalkylene polyol. It is preferable in terms of compatibility.
第一組成物においては、硬化性オリゴマー(A)が、ポリオキシアルキレンポリオールおよびポリイソシアネートを原料に用いて合成されたウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、ポリオキシアルキレンポリオールであることが、相溶性の点で好ましい。 Specifically, it is preferable to use a compound having a hydroxyl group (hereinafter referred to as a hydroxyl group-containing compound) as a raw material for the curable oligomer (A) and to use the same hydroxyl group-containing compound as the non-curable oligomer (C). .
In the first composition, the curable oligomer (A) is a urethane acrylate oligomer synthesized using polyoxyalkylene polyol and polyisocyanate as raw materials, and the non-curable oligomer (C) is a polyoxyalkylene polyol. It is preferable in terms of compatibility.
硬化性オリゴマー(A)の原料として用いる水酸基含有化合物と、非硬化性オリゴマー(C)として用いる水酸基含有化合物が同一でない場合でも、これら水酸基含有化合物は、互いに分子鎖が共通の構成単位(オキシアルキレン単位、ジエン単位等)を有する等、部分的に共通の構造を有し、極性が同程度であることが好ましい。硬化性オリゴマー(A)と非硬化性オリゴマー(C)とが同一の分子構造を部分的にでも有していれば、第一組成物中の非硬化性オリゴマー(C)の相溶性がより高まる。
Even when the hydroxyl group-containing compound used as the raw material of the curable oligomer (A) and the hydroxyl group-containing compound used as the non-curable oligomer (C) are not the same, these hydroxyl group-containing compounds are structural units having a common molecular chain (oxyalkylene). It is preferable that they have a partially common structure, such as having units and diene units, and have the same polarity. If the curable oligomer (A) and the non-curable oligomer (C) partially have the same molecular structure, the compatibility of the non-curable oligomer (C) in the first composition is further increased. .
硬化性オリゴマー(A)の原料として用いる水酸基含有化合物と、非硬化性オリゴマー(C)として用いる水酸基含有化合物が同一でない場合の好ましい組み合わせとしては、下記の組み合わせが挙げられる。
硬化性オリゴマー(A)が、オキシプロピレン基の一部をオキシエチレン基で置換したポリオキシプロピレンポリオールと、ポリイソシアネートとを原料に用いて合成されたウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、オキシエチレン基を有しないポリオキシプロピレンポリオールであって、水酸基1個当たりの分子量が硬化性オリゴマー(A)に用いたポリオールよりも小さいポリオキシプロピレンポリオールである組み合わせ。 Preferred combinations when the hydroxyl group-containing compound used as the raw material for the curable oligomer (A) and the hydroxyl group-containing compound used as the non-curable oligomer (C) are not the same include the following combinations.
The curable oligomer (A) is a urethane acrylate oligomer synthesized using a polyoxypropylene polyol in which a part of the oxypropylene group is substituted with an oxyethylene group and a polyisocyanate as raw materials, and a non-curable oligomer (C ) Is a polyoxypropylene polyol having no oxyethylene group, and is a polyoxypropylene polyol having a molecular weight per hydroxyl group smaller than that of the polyol used in the curable oligomer (A).
硬化性オリゴマー(A)が、オキシプロピレン基の一部をオキシエチレン基で置換したポリオキシプロピレンポリオールと、ポリイソシアネートとを原料に用いて合成されたウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、オキシエチレン基を有しないポリオキシプロピレンポリオールであって、水酸基1個当たりの分子量が硬化性オリゴマー(A)に用いたポリオールよりも小さいポリオキシプロピレンポリオールである組み合わせ。 Preferred combinations when the hydroxyl group-containing compound used as the raw material for the curable oligomer (A) and the hydroxyl group-containing compound used as the non-curable oligomer (C) are not the same include the following combinations.
The curable oligomer (A) is a urethane acrylate oligomer synthesized using a polyoxypropylene polyol in which a part of the oxypropylene group is substituted with an oxyethylene group and a polyisocyanate as raw materials, and a non-curable oligomer (C ) Is a polyoxypropylene polyol having no oxyethylene group, and is a polyoxypropylene polyol having a molecular weight per hydroxyl group smaller than that of the polyol used in the curable oligomer (A).
硬化性オリゴマー(A)と非硬化性オリゴマー(C)との組み合わせとしては、下記の組み合わせが特に好ましい。
硬化性オリゴマー(A)が、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンジオールと、ポリイソシアネートとを反応させて末端にイソシアネート基を有するプレポリマーを得た後、モノマー(a1)を反応させて得られるウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、硬化性オリゴマー(A)に用いたものと同じ、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンジオール、またはオキシプロピレン基を有するポリオキシプロピレンジオールであって、分子量が硬化性オリゴマー(A)に用いたジオールよりも小さいポリオキシプロピレンジオールである組み合わせ。 As a combination of the curable oligomer (A) and the non-curable oligomer (C), the following combinations are particularly preferable.
The curable oligomer (A) is reacted with a polyoxyalkylene diol having an oxypropylene group and an oxyethylene group and a polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacted with a monomer (a1). A polyoxyalkylene diol having an oxypropylene group and an oxyethylene group, or an oxypropylene group, the same as that used for the curable oligomer (A). A combination of polyoxypropylene diols having a molecular weight smaller than that of the diol used in the curable oligomer (A).
硬化性オリゴマー(A)が、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンジオールと、ポリイソシアネートとを反応させて末端にイソシアネート基を有するプレポリマーを得た後、モノマー(a1)を反応させて得られるウレタンアクリレートオリゴマーであり、非硬化性オリゴマー(C)が、硬化性オリゴマー(A)に用いたものと同じ、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンジオール、またはオキシプロピレン基を有するポリオキシプロピレンジオールであって、分子量が硬化性オリゴマー(A)に用いたジオールよりも小さいポリオキシプロピレンジオールである組み合わせ。 As a combination of the curable oligomer (A) and the non-curable oligomer (C), the following combinations are particularly preferable.
The curable oligomer (A) is reacted with a polyoxyalkylene diol having an oxypropylene group and an oxyethylene group and a polyisocyanate to obtain a prepolymer having an isocyanate group at the terminal, and then reacted with a monomer (a1). A polyoxyalkylene diol having an oxypropylene group and an oxyethylene group, or an oxypropylene group, the same as that used for the curable oligomer (A). A combination of polyoxypropylene diols having a molecular weight smaller than that of the diol used in the curable oligomer (A).
光重合開始剤(D)について:
光重合開始剤(D)としては、アセトフェノン系、ケタール系、ベンゾイン系、ベンゾインエーテル系、フォスフィンオキサイド系、ベンゾフェノン系、チオキサントン系、キノン系等の光重合開始剤が挙げられる。光重合開始剤(D)としては、フォスフィンオキサイド系、チオキサントン系の光重合開始剤が好ましく、光重合反応後に着色を抑える点から、フォスフィンオキサイド系が特に好ましい。 About photopolymerization initiator (D):
Examples of the photopolymerization initiator (D) include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators. As the photopolymerization initiator (D), phosphine oxide and thioxanthone photopolymerization initiators are preferable, and phosphine oxide is particularly preferable from the viewpoint of suppressing coloring after the photopolymerization reaction.
光重合開始剤(D)としては、アセトフェノン系、ケタール系、ベンゾイン系、ベンゾインエーテル系、フォスフィンオキサイド系、ベンゾフェノン系、チオキサントン系、キノン系等の光重合開始剤が挙げられる。光重合開始剤(D)としては、フォスフィンオキサイド系、チオキサントン系の光重合開始剤が好ましく、光重合反応後に着色を抑える点から、フォスフィンオキサイド系が特に好ましい。 About photopolymerization initiator (D):
Examples of the photopolymerization initiator (D) include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators. As the photopolymerization initiator (D), phosphine oxide and thioxanthone photopolymerization initiators are preferable, and phosphine oxide is particularly preferable from the viewpoint of suppressing coloring after the photopolymerization reaction.
添加剤について:
添加剤としては、重合禁止剤、光硬化促進剤、連鎖移動剤、光安定剤(紫外線吸収剤、ラジカル捕獲剤等)、酸化防止剤、難燃化剤、密着性向上剤(シランカップリング剤等)、顔料、染料等が挙げられる。第一組成物に添加する添加剤としては、重合禁止剤、光安定剤が好ましい。特に、重合開始剤より少ない量の重合禁止剤を含ませることによって、第一組成物の貯蔵安定性を改善でき、第一組成物の硬化物の分子量も調整できる。 About additives:
Additives include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (ultraviolet absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion improvers (silane coupling agents) Etc.), pigments, dyes and the like. As an additive added to the first composition, a polymerization inhibitor and a light stabilizer are preferable. In particular, the storage stability of the first composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the first composition can also be adjusted.
添加剤としては、重合禁止剤、光硬化促進剤、連鎖移動剤、光安定剤(紫外線吸収剤、ラジカル捕獲剤等)、酸化防止剤、難燃化剤、密着性向上剤(シランカップリング剤等)、顔料、染料等が挙げられる。第一組成物に添加する添加剤としては、重合禁止剤、光安定剤が好ましい。特に、重合開始剤より少ない量の重合禁止剤を含ませることによって、第一組成物の貯蔵安定性を改善でき、第一組成物の硬化物の分子量も調整できる。 About additives:
Additives include polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (ultraviolet absorbers, radical scavengers, etc.), antioxidants, flame retardants, adhesion improvers (silane coupling agents) Etc.), pigments, dyes and the like. As an additive added to the first composition, a polymerization inhibitor and a light stabilizer are preferable. In particular, the storage stability of the first composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the first composition can also be adjusted.
重合禁止剤としては、ヒドロキノン系(2,5-ジ-tert-ブチルヒドロキノン等)、カテコール系(p-tert-ブチルカテコール等)、アンスラキノン系、フェノチアジン系、ヒドロキシトルエン系等の重合禁止剤が挙げられる。
光安定剤としては、紫外線吸収剤(ベンゾトリアゾール系、ベンゾフェノン系、サリチレート系等)、ラジカル捕獲剤(ヒンダードアミン系)等が挙げられる。
酸化防止剤としては、ヒンダードフェノール系、リン系、イオウ系の化合物等が挙げられる。 Polymerization inhibitors include hydroquinone (2,5-di-tert-butylhydroquinone, etc.), catechol (p-tert-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene, and the like. Can be mentioned.
Examples of the light stabilizer include ultraviolet absorbers (benzotriazole series, benzophenone series, salicylate series, etc.), radical scavengers (hindered amine series), and the like.
Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, and sulfur compounds.
光安定剤としては、紫外線吸収剤(ベンゾトリアゾール系、ベンゾフェノン系、サリチレート系等)、ラジカル捕獲剤(ヒンダードアミン系)等が挙げられる。
酸化防止剤としては、ヒンダードフェノール系、リン系、イオウ系の化合物等が挙げられる。 Polymerization inhibitors include hydroquinone (2,5-di-tert-butylhydroquinone, etc.), catechol (p-tert-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene, and the like. Can be mentioned.
Examples of the light stabilizer include ultraviolet absorbers (benzotriazole series, benzophenone series, salicylate series, etc.), radical scavengers (hindered amine series), and the like.
Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, and sulfur compounds.
各原料の配合比について:
第一組成物における低分子量重合性化合物(B)の割合は、硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計(100質量%)のうち、1~80質量%が好ましく、3~70質量%がより好ましい。
低分子量重合性化合物(B1)の割合が前記下限値以上であれば、第一組成物の貯蔵安定性が良好になり、かつ粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好になる。
低分子量重合性化合物(B2)の割合は、第一組成物における硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計(100質量%)のうち、50質量%以下が好ましく、40質量%以下がより好ましい。 About the mixing ratio of each raw material:
The proportion of the low molecular weight polymerizable compound (B) in the first composition is preferably 1 to 80% by mass in the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 3 to 70% by mass is more preferable.
If the ratio of a low molecular weight polymeric compound (B1) is more than the said lower limit, the storage stability of a 1st composition will become favorable, and the adhesiveness of an adhesion layer and a transparent surface material, and an adhesion layer and to-be-adhered Adhesion with compound (display panel, etc.) is improved.
The proportion of the low molecular weight polymerizable compound (B2) is preferably 50% by mass or less of the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B) in the first composition. The mass% or less is more preferable.
第一組成物における低分子量重合性化合物(B)の割合は、硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計(100質量%)のうち、1~80質量%が好ましく、3~70質量%がより好ましい。
低分子量重合性化合物(B1)の割合が前記下限値以上であれば、第一組成物の貯蔵安定性が良好になり、かつ粘着層と透明面材との密着性、および粘着層と被貼合物(表示パネル等)との密着性が良好になる。
低分子量重合性化合物(B2)の割合は、第一組成物における硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計(100質量%)のうち、50質量%以下が好ましく、40質量%以下がより好ましい。 About the mixing ratio of each raw material:
The proportion of the low molecular weight polymerizable compound (B) in the first composition is preferably 1 to 80% by mass in the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 3 to 70% by mass is more preferable.
If the ratio of a low molecular weight polymeric compound (B1) is more than the said lower limit, the storage stability of a 1st composition will become favorable, and the adhesiveness of an adhesion layer and a transparent surface material, and an adhesion layer and to-be-adhered Adhesion with compound (display panel, etc.) is improved.
The proportion of the low molecular weight polymerizable compound (B2) is preferably 50% by mass or less of the total (100% by mass) of the curable oligomer (A) and the low molecular weight polymerizable compound (B) in the first composition. The mass% or less is more preferable.
なお、硬化性オリゴマー(A11)または硬化性オリゴマー(A21)の合成において、プレポリマーのイソシアネート基と反応したモノマー(a1)は、硬化性オリゴマー(A)の一部として存在するため、低分子量重合性化合物(B)の割合には含めない。一方、硬化性オリゴマー(A11)または硬化性オリゴマー(A21)の合成時または合成後に希釈剤として、必要に応じて添加する低分子量重合性化合物(ただし、プレポリマーと反応しないもの。)が、低分子量重合性化合物(B)に該当する場合、当該低分子量重合性化合物は、低分子量重合性化合物(B)の割合に含める。
In the synthesis of the curable oligomer (A11) or the curable oligomer (A21), the monomer (a1) that has reacted with the isocyanate group of the prepolymer exists as a part of the curable oligomer (A), so that low molecular weight polymerization is performed. Not included in the ratio of the active compound (B). On the other hand, a low molecular weight polymerizable compound (however, which does not react with the prepolymer) added as a diluent as a diluent during or after the synthesis of the curable oligomer (A11) or the curable oligomer (A21) is low. When falling under the molecular weight polymerizable compound (B), the low molecular weight polymerizable compound is included in the ratio of the low molecular weight polymerizable compound (B).
第一組成物が非硬化性オリゴマー(C)を含む場合、非硬化性オリゴマー(C)の割合は、第一組成物(100質量%)中、1~60質量%が好ましい。非硬化性オリゴマー(C)の割合が前記下限値以上であれば、粘着層と被貼合物との間に気泡が残存しにくい。非硬化性オリゴマー(C)の割合が前記上限値以下であれば、粘着層が充分に硬化すれば、粘着層から保護フィルムを剥離することが容易になる。
When the first composition contains the non-curable oligomer (C), the proportion of the non-curable oligomer (C) is preferably 1 to 60% by mass in the first composition (100% by mass). If the ratio of a non-curable oligomer (C) is more than the said lower limit, a bubble will not remain easily between an adhesion layer and a to-be-bonded thing. If the ratio of a non-curable oligomer (C) is below the said upper limit, if a pressure sensitive adhesive layer fully hardens, it will become easy to peel a protective film from a pressure sensitive adhesive layer.
第一組成物が非硬化性オリゴマー(C)を含む場合、硬化性オリゴマー(A)、低分子量重合性化合物(B)および非硬化性オリゴマー(C)の合計(100質量%)のうち、硬化性オリゴマー(A)が6~80質量%、低分子量重合性化合物(B)が3~70質量%、非硬化性オリゴマー(C)が1~60質量%であることが好ましく、硬化性オリゴマー(A)が6~60質量%、低分子量重合性化合物(B)が3~55質量%、非硬化性オリゴマー(C)が1~60質量%であることがより好ましい。
In the case where the first composition contains a non-curable oligomer (C), curing is performed out of the total (100% by mass) of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C). The curable oligomer (A) is preferably 6 to 80% by mass, the low molecular weight polymerizable compound (B) is preferably 3 to 70% by mass, and the non-curable oligomer (C) is preferably 1 to 60% by mass. More preferably, A) is 6 to 60% by mass, the low molecular weight polymerizable compound (B) is 3 to 55% by mass, and the non-curable oligomer (C) is 1 to 60% by mass.
第一組成物における光重合開始剤(D)の配合量は、硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計100質量部に対して、0.01~10質量部が好ましく、0.1~5質量部がより好ましい。
第一組成物における添加剤の配合量は、硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計100質量部に対して、10質量部以下が好ましく、5質量部以下がより好ましい。 The blending amount of the photopolymerization initiator (D) in the first composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 0.1 to 5 parts by mass is more preferable.
The compounding amount of the additive in the first composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). .
第一組成物における添加剤の配合量は、硬化性オリゴマー(A)および低分子量重合性化合物(B)の合計100質量部に対して、10質量部以下が好ましく、5質量部以下がより好ましい。 The blending amount of the photopolymerization initiator (D) in the first composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). 0.1 to 5 parts by mass is more preferable.
The compounding amount of the additive in the first composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the curable oligomer (A) and the low molecular weight polymerizable compound (B). .
第一組成物の粘度について:
第一組成物の粘度は、0.05~50Pa・sが好ましく、1~20Pa・sがより好ましい。第一組成物の粘度が0.05Pa・s以上であれば、粘着層を形成する際に、第一組成物の塗布形状が保持される。第一組成物の粘度が50Pa・s以下であれば、透明面材の表面に第一組成物を供給しやすく、粘着層付き透明面材の生産性がよい。 Regarding the viscosity of the first composition:
The viscosity of the first composition is preferably 0.05 to 50 Pa · s, more preferably 1 to 20 Pa · s. If the viscosity of the first composition is 0.05 Pa · s or more, the application shape of the first composition is maintained when the adhesive layer is formed. If the viscosity of the first composition is 50 Pa · s or less, it is easy to supply the first composition to the surface of the transparent surface material, and the productivity of the transparent surface material with an adhesive layer is good.
第一組成物の粘度は、0.05~50Pa・sが好ましく、1~20Pa・sがより好ましい。第一組成物の粘度が0.05Pa・s以上であれば、粘着層を形成する際に、第一組成物の塗布形状が保持される。第一組成物の粘度が50Pa・s以下であれば、透明面材の表面に第一組成物を供給しやすく、粘着層付き透明面材の生産性がよい。 Regarding the viscosity of the first composition:
The viscosity of the first composition is preferably 0.05 to 50 Pa · s, more preferably 1 to 20 Pa · s. If the viscosity of the first composition is 0.05 Pa · s or more, the application shape of the first composition is maintained when the adhesive layer is formed. If the viscosity of the first composition is 50 Pa · s or less, it is easy to supply the first composition to the surface of the transparent surface material, and the productivity of the transparent surface material with an adhesive layer is good.
(堰)
堰は、液状の堰形成用硬化性樹脂組成物を塗布し、硬化してなる透明樹脂からなる部分である。 (Weir)
The weir is a portion made of a transparent resin formed by applying and curing a liquid curable resin composition for forming a weir.
堰は、液状の堰形成用硬化性樹脂組成物を塗布し、硬化してなる透明樹脂からなる部分である。 (Weir)
The weir is a portion made of a transparent resin formed by applying and curing a liquid curable resin composition for forming a weir.
粘着層の周縁に堰を有することによって、粘着層の周縁部が外方へ拡がって周縁部が薄肉化することが抑えられ、粘着層の全体の厚さを均一に保つことができる。粘着層の全体の厚さを均一にすることで、被貼合物(たとえば、表示パネル等)との貼合において、その界面に気泡が残留することを抑制しやすく好ましい。
By having a weir around the periphery of the adhesive layer, it is possible to suppress the peripheral portion of the adhesive layer from spreading outward and thinning of the peripheral portion, and to keep the entire thickness of the adhesive layer uniform. By making the whole thickness of the pressure-sensitive adhesive layer uniform, it is preferable that air bubbles remain at the interface in bonding with an object to be bonded (for example, a display panel or the like).
堰を有する場合、堰の厚さが粘着層の厚さよりも僅かに厚くなっている。粘着層の表面が平坦でなく、粘着層の厚さが一定でなかったとしても、堰が粘着層と近接する領域の少なくとも一部において、堰の厚さが粘着層の厚さよりも僅かに大きいことが好ましい。
When it has a weir, the thickness of the weir is slightly thicker than the thickness of the adhesive layer. Even if the surface of the adhesive layer is not flat and the thickness of the adhesive layer is not constant, the thickness of the weir is slightly larger than the thickness of the adhesive layer in at least a part of the area where the weir is adjacent to the adhesive layer It is preferable.
堰の厚さは、堰と粘着層とが近接する領域を除いた粘着層の平均厚さとほぼ等しいか、または前述のように、粘着層の厚さより0.005~0.05mm厚いことが好ましく、0.01~0.03mm厚いことがより好ましい。
The thickness of the weir is preferably approximately equal to the average thickness of the adhesive layer excluding the area where the weir and the adhesive layer are close to each other, or, as described above, 0.005 to 0.05 mm thicker than the thickness of the adhesive layer. More preferably, the thickness is 0.01 to 0.03 mm thick.
表示パネルの画像表示領域の外側の領域が比較的狭いため、堰の幅は狭くすることが好ましい。堰の幅は、0.5~2mmが好ましく、0.8~1.6mmがより好ましい。
Since the area outside the image display area of the display panel is relatively narrow, the width of the weir is preferably narrow. The width of the weir is preferably 0.5 to 2 mm, more preferably 0.8 to 1.6 mm.
堰の35℃における貯蔵せん断弾性率は、粘着層の35℃における貯蔵せん断弾性率よりも大きいことが好ましい。堰の貯蔵せん断弾性率が、粘着層の貯蔵せん断弾性率よりも大きければ、被貼合物と粘着層付き透明面材とを貼合する際に、粘着層の周縁部において、被貼合物と粘着層との界面に気泡が残存していても、気泡が外部に開放されにくく、独立した気泡となりやすい。
よって、減圧雰囲気下にて被貼合物と粘着層付き透明面材とを貼合した後、これを大気圧雰囲気下に戻した際に、気泡内の圧力(すなわち、減圧雰囲気の減圧のままの状態の圧力)と粘着層にかかる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧によって気泡の体積が減少し、気泡は消滅しやすい。
また、堰の貯蔵せん断弾性率を、粘着層の貯蔵せん断弾性率よりも大きくすることで、堰が粘着層と近接する領域の少なくとも一部において、堰の厚さが粘着層の厚さよりも僅かに大きい、粘着層付き透明面材を製造しやすくなる。 The storage shear modulus at 35 ° C. of the weir is preferably larger than the storage shear modulus at 35 ° C. of the adhesive layer. When the storage shear elastic modulus of the weir is larger than the storage shear elastic modulus of the adhesive layer, the object to be bonded is bonded at the periphery of the adhesive layer when the object to be bonded and the transparent surface material with the adhesive layer are bonded. Even if air bubbles remain at the interface between the adhesive layer and the adhesive layer, the air bubbles are not easily released to the outside, and become independent air bubbles.
Therefore, after bonding the object to be bonded and the transparent surface with the adhesive layer in a reduced pressure atmosphere, when this is returned to the atmospheric pressure atmosphere, the pressure inside the bubbles (that is, the reduced pressure of the reduced pressure atmosphere remains ) And the pressure applied to the adhesive layer (that is, the atmospheric pressure when the pressure is returned to the atmospheric pressure), the volume of the bubbles is reduced, and the bubbles tend to disappear.
Further, by making the storage shear modulus of the weir larger than the storage shear modulus of the adhesive layer, the thickness of the weir is slightly smaller than the thickness of the adhesive layer in at least a part of the region where the weir is close to the adhesive layer. It is easy to produce a transparent face material with a large adhesive layer.
よって、減圧雰囲気下にて被貼合物と粘着層付き透明面材とを貼合した後、これを大気圧雰囲気下に戻した際に、気泡内の圧力(すなわち、減圧雰囲気の減圧のままの状態の圧力)と粘着層にかかる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧によって気泡の体積が減少し、気泡は消滅しやすい。
また、堰の貯蔵せん断弾性率を、粘着層の貯蔵せん断弾性率よりも大きくすることで、堰が粘着層と近接する領域の少なくとも一部において、堰の厚さが粘着層の厚さよりも僅かに大きい、粘着層付き透明面材を製造しやすくなる。 The storage shear modulus at 35 ° C. of the weir is preferably larger than the storage shear modulus at 35 ° C. of the adhesive layer. When the storage shear elastic modulus of the weir is larger than the storage shear elastic modulus of the adhesive layer, the object to be bonded is bonded at the periphery of the adhesive layer when the object to be bonded and the transparent surface material with the adhesive layer are bonded. Even if air bubbles remain at the interface between the adhesive layer and the adhesive layer, the air bubbles are not easily released to the outside, and become independent air bubbles.
Therefore, after bonding the object to be bonded and the transparent surface with the adhesive layer in a reduced pressure atmosphere, when this is returned to the atmospheric pressure atmosphere, the pressure inside the bubbles (that is, the reduced pressure of the reduced pressure atmosphere remains ) And the pressure applied to the adhesive layer (that is, the atmospheric pressure when the pressure is returned to the atmospheric pressure), the volume of the bubbles is reduced, and the bubbles tend to disappear.
Further, by making the storage shear modulus of the weir larger than the storage shear modulus of the adhesive layer, the thickness of the weir is slightly smaller than the thickness of the adhesive layer in at least a part of the region where the weir is close to the adhesive layer. It is easy to produce a transparent face material with a large adhesive layer.
(堰形成用硬化性樹脂組成物)
堰形成用硬化性樹脂組成物としては、たとえば、シリコーン樹脂(オルガノポリシロキサン)、ウレタンオリゴマー、ウレタンアクリレートオリゴマー等を含む組成物が挙げられる。
堰形成用硬化性樹脂組成物としては、柔軟性、硬化速度の点から、オリゴマー(F)およびモノマー(G)を含む組成物(以下、第二組成物と記す。)が好ましい。 (Curable resin composition for weir formation)
Examples of the curable resin composition for weir formation include a composition containing a silicone resin (organopolysiloxane), a urethane oligomer, a urethane acrylate oligomer, and the like.
As the weir-forming curable resin composition, a composition containing an oligomer (F) and a monomer (G) (hereinafter referred to as a second composition) is preferable from the viewpoints of flexibility and curing speed.
堰形成用硬化性樹脂組成物としては、たとえば、シリコーン樹脂(オルガノポリシロキサン)、ウレタンオリゴマー、ウレタンアクリレートオリゴマー等を含む組成物が挙げられる。
堰形成用硬化性樹脂組成物としては、柔軟性、硬化速度の点から、オリゴマー(F)およびモノマー(G)を含む組成物(以下、第二組成物と記す。)が好ましい。 (Curable resin composition for weir formation)
Examples of the curable resin composition for weir formation include a composition containing a silicone resin (organopolysiloxane), a urethane oligomer, a urethane acrylate oligomer, and the like.
As the weir-forming curable resin composition, a composition containing an oligomer (F) and a monomer (G) (hereinafter referred to as a second composition) is preferable from the viewpoints of flexibility and curing speed.
(第二組成物)
第二組成物は、光硬化性樹脂組成物であってもよく、熱硬化性樹脂組成物であってもよい。第二組成物としては、低温で硬化でき、かつ硬化速度が速い点から、光重合開始剤(E)がさらに配合された光硬化性樹脂組成物であることが好ましい。また、第二組成物が光硬化性樹脂組成物であれば、硬化には高い温度を必要としないことから、高温による表示パネルの損傷のおそれも少ない。
また、第二組成物として、第一組成物と同様の組成のものを用いてもよい。この場合、後述する工程(α21)において、第二組成物を透明面材の表面の周縁部に塗布して半硬化させて堰とする。 (Second composition)
The second composition may be a photocurable resin composition or a thermosetting resin composition. As a 2nd composition, it is preferable that it is a photocurable resin composition with which the photoinitiator (E) was further mix | blended from the point which can be hardened | cured at low temperature and a cure rate is quick. In addition, if the second composition is a photocurable resin composition, a high temperature is not required for curing, so there is little risk of damage to the display panel due to high temperatures.
Moreover, you may use the thing of the same composition as a 1st composition as a 2nd composition. In this case, in the step (α21) to be described later, the second composition is applied to the peripheral edge of the surface of the transparent face material and semi-cured to form a weir.
第二組成物は、光硬化性樹脂組成物であってもよく、熱硬化性樹脂組成物であってもよい。第二組成物としては、低温で硬化でき、かつ硬化速度が速い点から、光重合開始剤(E)がさらに配合された光硬化性樹脂組成物であることが好ましい。また、第二組成物が光硬化性樹脂組成物であれば、硬化には高い温度を必要としないことから、高温による表示パネルの損傷のおそれも少ない。
また、第二組成物として、第一組成物と同様の組成のものを用いてもよい。この場合、後述する工程(α21)において、第二組成物を透明面材の表面の周縁部に塗布して半硬化させて堰とする。 (Second composition)
The second composition may be a photocurable resin composition or a thermosetting resin composition. As a 2nd composition, it is preferable that it is a photocurable resin composition with which the photoinitiator (E) was further mix | blended from the point which can be hardened | cured at low temperature and a cure rate is quick. In addition, if the second composition is a photocurable resin composition, a high temperature is not required for curing, so there is little risk of damage to the display panel due to high temperatures.
Moreover, you may use the thing of the same composition as a 1st composition as a 2nd composition. In this case, in the step (α21) to be described later, the second composition is applied to the peripheral edge of the surface of the transparent face material and semi-cured to form a weir.
第二組成物には、必要に応じて、添加剤が配合されていてもよい。
また、透明面材と表示パネルとの間隔を保持するために、所定の粒子径のスペーサ粒子を第二組成物に配合してもよい。 The second composition may contain an additive as necessary.
Moreover, in order to maintain the space | interval of a transparent surface material and a display panel, you may mix | blend the spacer particle | grains of a predetermined particle diameter with a 2nd composition.
また、透明面材と表示パネルとの間隔を保持するために、所定の粒子径のスペーサ粒子を第二組成物に配合してもよい。 The second composition may contain an additive as necessary.
Moreover, in order to maintain the space | interval of a transparent surface material and a display panel, you may mix | blend the spacer particle | grains of a predetermined particle diameter with a 2nd composition.
オリゴマー(F)について:
オリゴマー(F)は、付加重合性不飽和二重結合を有し、かつ数平均分子量が30,000~100,000の化合物である。 About oligomer (F):
The oligomer (F) is a compound having an addition polymerizable unsaturated double bond and a number average molecular weight of 30,000 to 100,000.
オリゴマー(F)は、付加重合性不飽和二重結合を有し、かつ数平均分子量が30,000~100,000の化合物である。 About oligomer (F):
The oligomer (F) is a compound having an addition polymerizable unsaturated double bond and a number average molecular weight of 30,000 to 100,000.
オリゴマー(F)が有する付加重合性不飽和二重結合としては、アクリロイルオキシ基、メタクリロイルオキシ基等が挙げられる。オリゴマー(F)の付加重合性不飽和二重結合としては、硬化速度が速い点および透明性の高い堰が得られる点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましい。また、オリゴマー(F)とモノマー(G)との付加重合性不飽和二重結合の反応性の差が小さくなり、均質な堰を形成できる点から、オリゴマー(F)が有する付加重合性不飽和二重結合がアクリロイルオキシ基であり、モノマー(G)が有する付加重合性不飽和二重結合がメタクリロイルオキシ基であることが特に好ましい。
Examples of the addition polymerizable unsaturated double bond of the oligomer (F) include an acryloyloxy group and a methacryloyloxy group. As the addition polymerizable unsaturated double bond of the oligomer (F), an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint that a curing rate is high and a highly transparent weir is obtained. Moreover, the difference in the reactivity of the addition polymerizable unsaturated double bond between the oligomer (F) and the monomer (G) is reduced, and a homogeneous weir can be formed. It is particularly preferable that the double bond is an acryloyloxy group and the addition polymerizable unsaturated double bond of the monomer (G) is a methacryloyloxy group.
オリゴマー(F)の数平均分子量は、30,000~100,000であり、40,000~80,000が好ましく、50,000~65,000がより好ましい。オリゴマー(F)の数平均分子量が前記範囲内であれば、第二組成物の粘度を後述する範囲に調整しやすい。
オリゴマー(F)の付加重合性不飽和二重結合の平均数は、第二組成物の硬化性および堰の機械的特性の点から、1.8~4が好ましい。 The number average molecular weight of the oligomer (F) is 30,000 to 100,000, preferably 40,000 to 80,000, more preferably 50,000 to 65,000. If the number average molecular weight of an oligomer (F) is in the said range, it will be easy to adjust the viscosity of a 2nd composition to the range mentioned later.
The average number of addition polymerizable unsaturated double bonds of the oligomer (F) is preferably 1.8 to 4 from the viewpoint of the curability of the second composition and the mechanical properties of the weir.
オリゴマー(F)の付加重合性不飽和二重結合の平均数は、第二組成物の硬化性および堰の機械的特性の点から、1.8~4が好ましい。 The number average molecular weight of the oligomer (F) is 30,000 to 100,000, preferably 40,000 to 80,000, more preferably 50,000 to 65,000. If the number average molecular weight of an oligomer (F) is in the said range, it will be easy to adjust the viscosity of a 2nd composition to the range mentioned later.
The average number of addition polymerizable unsaturated double bonds of the oligomer (F) is preferably 1.8 to 4 from the viewpoint of the curability of the second composition and the mechanical properties of the weir.
オリゴマー(F)としては、ウレタン結合を有するウレタンオリゴマー、ポリオキシアルキレンポリオールのポリ(メタ)アクリレート、ポリエステルポリオールのポリ(メタ)アクリレート等が挙げられる。
ウレタン鎖の分子設計等によって硬化後の堰の機械的特性、透明面材との密着性等を幅広く調整できる点から、ポリオールおよびポリイソシアネートを原料に用いて合成されたウレタンオリゴマーが好ましく、後述する合成方法で得られるオリゴマー(F1)がより好ましい。ポリオールとしては、ポリオキシアルキレンポリオールがより好ましい。 Examples of the oligomer (F) include a urethane oligomer having a urethane bond, a poly (meth) acrylate of a polyoxyalkylene polyol, and a poly (meth) acrylate of a polyester polyol.
Urethane oligomers synthesized using polyols and polyisocyanates as raw materials are preferred from the viewpoint that the mechanical properties of the weir after curing, adhesion to the transparent surface material, and the like can be widely adjusted by molecular design of the urethane chain, which will be described later. The oligomer (F1) obtained by the synthesis method is more preferable. As the polyol, polyoxyalkylene polyol is more preferable.
ウレタン鎖の分子設計等によって硬化後の堰の機械的特性、透明面材との密着性等を幅広く調整できる点から、ポリオールおよびポリイソシアネートを原料に用いて合成されたウレタンオリゴマーが好ましく、後述する合成方法で得られるオリゴマー(F1)がより好ましい。ポリオールとしては、ポリオキシアルキレンポリオールがより好ましい。 Examples of the oligomer (F) include a urethane oligomer having a urethane bond, a poly (meth) acrylate of a polyoxyalkylene polyol, and a poly (meth) acrylate of a polyester polyol.
Urethane oligomers synthesized using polyols and polyisocyanates as raw materials are preferred from the viewpoint that the mechanical properties of the weir after curing, adhesion to the transparent surface material, and the like can be widely adjusted by molecular design of the urethane chain, which will be described later. The oligomer (F1) obtained by the synthesis method is more preferable. As the polyol, polyoxyalkylene polyol is more preferable.
オリゴマー(F1):
数平均分子量が30,000~100,000の範囲のオリゴマー(F1)は、高粘度となるため、通常の方法では合成が難しく、合成できたとしてもモノマー(G)との混合が難しい。
そのため、オリゴマー(F1)を、モノマー(G)(下記のモノマー(G1)およびモノマー(G2))を用いる合成方法で合成した後、得られた生成物をそのまま第二組成物として用いること、または得られた生成物をさらにモノマー(G)(下記のモノマー(G1)~モノマー(G3)等)で希釈して第二脂組成物として用いることが好ましい。
モノマー(G1):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつイソシアネート基と反応する基を有しないモノマー。
モノマー(G2):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつイソシアネート基と反応する基を有するモノマー。
モノマー(G3):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつ水酸基を有するモノマー。 Oligomer (F1):
Since the oligomer (F1) having a number average molecular weight in the range of 30,000 to 100,000 has a high viscosity, it is difficult to synthesize by a normal method, and even if synthesized, it is difficult to mix with the monomer (G).
Therefore, after synthesizing the oligomer (F1) by a synthesis method using the monomer (G) (the following monomer (G1) and monomer (G2)), the obtained product is used as it is as the second composition, or It is preferable that the obtained product is further diluted with a monomer (G) (the following monomers (G1) to monomer (G3), etc.) to be used as the second fat composition.
Monomer (G1): Monomer (G) that has an addition-polymerizable unsaturated double bond and does not have a group that reacts with an isocyanate group.
Monomer (G2): Monomer (G) having an addition polymerizable unsaturated double bond and a group that reacts with an isocyanate group.
Monomer (G3): Monomer (G) having an addition polymerizable unsaturated double bond and a hydroxyl group.
数平均分子量が30,000~100,000の範囲のオリゴマー(F1)は、高粘度となるため、通常の方法では合成が難しく、合成できたとしてもモノマー(G)との混合が難しい。
そのため、オリゴマー(F1)を、モノマー(G)(下記のモノマー(G1)およびモノマー(G2))を用いる合成方法で合成した後、得られた生成物をそのまま第二組成物として用いること、または得られた生成物をさらにモノマー(G)(下記のモノマー(G1)~モノマー(G3)等)で希釈して第二脂組成物として用いることが好ましい。
モノマー(G1):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつイソシアネート基と反応する基を有しないモノマー。
モノマー(G2):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつイソシアネート基と反応する基を有するモノマー。
モノマー(G3):モノマー(G)のうち、付加重合性不飽和二重結合を有し、かつ水酸基を有するモノマー。 Oligomer (F1):
Since the oligomer (F1) having a number average molecular weight in the range of 30,000 to 100,000 has a high viscosity, it is difficult to synthesize by a normal method, and even if synthesized, it is difficult to mix with the monomer (G).
Therefore, after synthesizing the oligomer (F1) by a synthesis method using the monomer (G) (the following monomer (G1) and monomer (G2)), the obtained product is used as it is as the second composition, or It is preferable that the obtained product is further diluted with a monomer (G) (the following monomers (G1) to monomer (G3), etc.) to be used as the second fat composition.
Monomer (G1): Monomer (G) that has an addition-polymerizable unsaturated double bond and does not have a group that reacts with an isocyanate group.
Monomer (G2): Monomer (G) having an addition polymerizable unsaturated double bond and a group that reacts with an isocyanate group.
Monomer (G3): Monomer (G) having an addition polymerizable unsaturated double bond and a hydroxyl group.
オリゴマー(F1)は、下記の合成方法によって得られる。
希釈剤として用いるモノマー(G1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、モノマー(G2)を反応させる方法。 The oligomer (F1) is obtained by the following synthesis method.
A method in which a polyol and polyisocyanate are reacted in the presence of the monomer (G1) used as a diluent to obtain a prepolymer having an isocyanate group, and then the monomer (G2) is reacted with the isocyanate group of the prepolymer.
希釈剤として用いるモノマー(G1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、モノマー(G2)を反応させる方法。 The oligomer (F1) is obtained by the following synthesis method.
A method in which a polyol and polyisocyanate are reacted in the presence of the monomer (G1) used as a diluent to obtain a prepolymer having an isocyanate group, and then the monomer (G2) is reacted with the isocyanate group of the prepolymer.
ポリオールとしては、第一組成物で例示されたポリオールと同様のものが挙げられる。ポリオールは、第一組成物と同じものであってもよく、異なるものであってもよいが、同じものが好ましい。また、第二組成物の他の成分との相溶性を高める点から、オキシプロピレン基およびオキシエチレン基を有するポリオキシアルキレンポリオールがさらに好ましい。
ポリオールは、1種を単独で用いてもよく、2種以上を併用してもよい。 As a polyol, the thing similar to the polyol illustrated by the 1st composition is mentioned. The polyol may be the same as or different from the first composition, but the same is preferable. Moreover, the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 2nd composition.
A polyol may be used individually by 1 type and may use 2 or more types together.
ポリオールは、1種を単独で用いてもよく、2種以上を併用してもよい。 As a polyol, the thing similar to the polyol illustrated by the 1st composition is mentioned. The polyol may be the same as or different from the first composition, but the same is preferable. Moreover, the polyoxyalkylene polyol which has an oxypropylene group and an oxyethylene group is more preferable from the point which improves compatibility with the other component of a 2nd composition.
A polyol may be used individually by 1 type and may use 2 or more types together.
ポリイソシアネートとしては、第一組成物で例示されたポリイソシアネートと同様のものが挙げられる。ポリイソシアネートは、第一組成物と同じものであってもよく、異なるものであってよいが、同じものが好ましい。
ポリイソシアネートは、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the polyisocyanate include the same polyisocyanates exemplified in the first composition. The polyisocyanate may be the same as or different from the first composition, but the same is preferable.
Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
ポリイソシアネートは、1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the polyisocyanate include the same polyisocyanates exemplified in the first composition. The polyisocyanate may be the same as or different from the first composition, but the same is preferable.
Polyisocyanate may be used individually by 1 type and may use 2 or more types together.
モノマー(G)について:
モノマー(G)は、付加重合性不飽和二重結合を有し、分子量が125~600の化合物である。 About monomer (G):
The monomer (G) is a compound having an addition polymerizable unsaturated double bond and a molecular weight of 125 to 600.
モノマー(G)は、付加重合性不飽和二重結合を有し、分子量が125~600の化合物である。 About monomer (G):
The monomer (G) is a compound having an addition polymerizable unsaturated double bond and a molecular weight of 125 to 600.
モノマー(G)が有する付加重合性不飽和二重結合としては、アクリロイルオキシ基、メタクリロイルオキシ基等が挙げられる。モノマー(G)の付加重合性不飽和二重結合としては、硬化速度が速い点および透明性の高い堰が得られる点から、アクリロイルオキシ基またはメタクリロイルオキシ基が好ましい。また、オリゴマー(F)とモノマー(G)との付加重合性不飽和二重結合の反応性の差が小さくなり、均質な堰を形成できる点から、オリゴマー(F)が有する付加重合性不飽和二重結合がアクリロイルオキシ基であり、モノマー(G)が有する付加重合性不飽和二重結合がメタクリロイルオキシ基であることが特に好ましい。
Examples of the addition polymerizable unsaturated double bond of the monomer (G) include an acryloyloxy group and a methacryloyloxy group. As the addition polymerizable unsaturated double bond of the monomer (G), an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint that a curing rate is high and a highly transparent weir is obtained. Moreover, the difference in the reactivity of the addition polymerizable unsaturated double bond between the oligomer (F) and the monomer (G) is reduced, and a homogeneous weir can be formed. It is particularly preferable that the double bond is an acryloyloxy group and the addition polymerizable unsaturated double bond of the monomer (G) is a methacryloyloxy group.
モノマー(G)の分子量は、125~600であり、140~400が好ましく、150~350がより好ましい。モノマー(G)の分子量が125以上であれば、表示装置を製造する際のモノマー(G)の揮発が抑えられる。モノマー(G)の分子量が600以下であれば、高分子量のオリゴマー(F)に対するモノマー(G)の溶解性を高めることができ、第二組成物としての粘度調整を好適に行える。
The molecular weight of the monomer (G) is 125 to 600, preferably 140 to 400, more preferably 150 to 350. If the molecular weight of the monomer (G) is 125 or more, volatilization of the monomer (G) when manufacturing the display device can be suppressed. If the molecular weight of a monomer (G) is 600 or less, the solubility of the monomer (G) with respect to the high molecular weight oligomer (F) can be improved, and the viscosity adjustment as a 2nd composition can be performed suitably.
モノマー(G)は、オリゴマー(F1)の合成方法において希釈剤として用いたモノマー(G1)を含んでいてもよい。また、モノマー(G)として、オリゴマー(F1)の合成方法に用いた未反応のモノマー(G2)を含んでいてもよい。
また、モノマー(G)は、透明面材と堰との密着性や添加剤の溶解性の点から、モノマー(G3)を含むことが好ましい。 The monomer (G) may contain the monomer (G1) used as a diluent in the synthesis method of the oligomer (F1). Moreover, the unreacted monomer (G2) used for the synthesis method of the oligomer (F1) may be included as the monomer (G).
Moreover, it is preferable that a monomer (G) contains a monomer (G3) from the point of the adhesiveness of a transparent surface material and a weir, and the solubility point of an additive.
また、モノマー(G)は、透明面材と堰との密着性や添加剤の溶解性の点から、モノマー(G3)を含むことが好ましい。 The monomer (G) may contain the monomer (G1) used as a diluent in the synthesis method of the oligomer (F1). Moreover, the unreacted monomer (G2) used for the synthesis method of the oligomer (F1) may be included as the monomer (G).
Moreover, it is preferable that a monomer (G) contains a monomer (G3) from the point of the adhesiveness of a transparent surface material and a weir, and the solubility point of an additive.
モノマー(G1):
モノマー(G1)としては、炭素数8~22のアルキル基を有するアルキル(メタ)アクリレート(n-ドデシル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート、n-ベヘニル(メタ)アクリレート等)、脂環式炭化水素基を有する(メタ)アクリレート(イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート等)が挙げられる。 Monomer (G1):
Monomers (G1) include alkyl (meth) acrylates having an alkyl group of 8 to 22 carbon atoms (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-behenyl (meth) acrylate, etc.)), fat Examples include (meth) acrylates having a cyclic hydrocarbon group (such as isobornyl (meth) acrylate and adamantyl (meth) acrylate).
モノマー(G1)としては、炭素数8~22のアルキル基を有するアルキル(メタ)アクリレート(n-ドデシル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート、n-ベヘニル(メタ)アクリレート等)、脂環式炭化水素基を有する(メタ)アクリレート(イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート等)が挙げられる。 Monomer (G1):
Monomers (G1) include alkyl (meth) acrylates having an alkyl group of 8 to 22 carbon atoms (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n-behenyl (meth) acrylate, etc.)), fat Examples include (meth) acrylates having a cyclic hydrocarbon group (such as isobornyl (meth) acrylate and adamantyl (meth) acrylate).
モノマー(G2):
モノマー(G2)としては、活性水素(水酸基、アミノ基等)および付加重合性不飽和二重結合を有するモノマーが挙げられる。モノマー(G2)の具体例としては、炭素数2~6のヒドロキシアルキル基を有するヒドロキシアルキル(メタ)アクリレート(2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等)等が挙げられる。モノマー(G2)としては、炭素数2~4のヒドロキシアルキル基を有するヒドロキシアルキルアクリレートが好ましい。 Monomer (G2):
Examples of the monomer (G2) include monomers having active hydrogen (hydroxyl group, amino group, etc.) and an addition polymerizable unsaturated double bond. Specific examples of the monomer (G2) include hydroxyalkyl (meth) acrylates having a C2-C6 hydroxyalkyl group (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl). (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.). As the monomer (G2), a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferable.
モノマー(G2)としては、活性水素(水酸基、アミノ基等)および付加重合性不飽和二重結合を有するモノマーが挙げられる。モノマー(G2)の具体例としては、炭素数2~6のヒドロキシアルキル基を有するヒドロキシアルキル(メタ)アクリレート(2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等)等が挙げられる。モノマー(G2)としては、炭素数2~4のヒドロキシアルキル基を有するヒドロキシアルキルアクリレートが好ましい。 Monomer (G2):
Examples of the monomer (G2) include monomers having active hydrogen (hydroxyl group, amino group, etc.) and an addition polymerizable unsaturated double bond. Specific examples of the monomer (G2) include hydroxyalkyl (meth) acrylates having a C2-C6 hydroxyalkyl group (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl). (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.). As the monomer (G2), a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferable.
モノマー(G3):
モノマー(G3)としては、水酸基数1~2、炭素数3~8のヒドロキシアルキル基を有するヒドロキシメタアクリレート(2-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、6-ヒドロキシヘキシルメタクリレート等)が好ましく、2-ヒドロキシブチルメタクリレートが特に好ましい。 Monomer (G3):
Monomers (G3) include hydroxy methacrylates having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl). Methacrylate) and the like are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.
モノマー(G3)としては、水酸基数1~2、炭素数3~8のヒドロキシアルキル基を有するヒドロキシメタアクリレート(2-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、6-ヒドロキシヘキシルメタクリレート等)が好ましく、2-ヒドロキシブチルメタクリレートが特に好ましい。 Monomer (G3):
Monomers (G3) include hydroxy methacrylates having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl). Methacrylate) and the like are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.
光重合開始剤(E)について:
光重合開始剤(E)としては、アセトフェノン系、ケタール系、ベンゾイン系、ベンゾインエーテル系、フォスフィンオキサイド系、ベンゾフェノン系、チオキサントン系、キノン系等の光重合開始剤が挙げられる。光重合開始剤(E)としては、アセトフェノン系、ケタール系、ベンゾインエーテル系の光重合開始剤が好ましい。短波長の可視光による硬化を行う場合は、吸収波長域の点から、フォスフィンオキサイド系の光重合開始剤がより好ましい。吸収波長域の異なる2種以上の光重合開始剤(E)を併用することによって、硬化時間をさらに速めたり、堰における表面硬化性を高めることができる。 About photopolymerization initiator (E):
Examples of the photopolymerization initiator (E) include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators. As the photopolymerization initiator (E), acetophenone-based, ketal-based, and benzoin ether-based photopolymerization initiators are preferable. When curing with visible light having a short wavelength, a phosphine oxide-based photopolymerization initiator is more preferable from the viewpoint of the absorption wavelength region. By using together two or more kinds of photopolymerization initiators (E) having different absorption wavelength ranges, the curing time can be further accelerated, or the surface curability at the weir can be enhanced.
光重合開始剤(E)としては、アセトフェノン系、ケタール系、ベンゾイン系、ベンゾインエーテル系、フォスフィンオキサイド系、ベンゾフェノン系、チオキサントン系、キノン系等の光重合開始剤が挙げられる。光重合開始剤(E)としては、アセトフェノン系、ケタール系、ベンゾインエーテル系の光重合開始剤が好ましい。短波長の可視光による硬化を行う場合は、吸収波長域の点から、フォスフィンオキサイド系の光重合開始剤がより好ましい。吸収波長域の異なる2種以上の光重合開始剤(E)を併用することによって、硬化時間をさらに速めたり、堰における表面硬化性を高めることができる。 About photopolymerization initiator (E):
Examples of the photopolymerization initiator (E) include acetophenone, ketal, benzoin, benzoin ether, phosphine oxide, benzophenone, thioxanthone, and quinone photopolymerization initiators. As the photopolymerization initiator (E), acetophenone-based, ketal-based, and benzoin ether-based photopolymerization initiators are preferable. When curing with visible light having a short wavelength, a phosphine oxide-based photopolymerization initiator is more preferable from the viewpoint of the absorption wavelength region. By using together two or more kinds of photopolymerization initiators (E) having different absorption wavelength ranges, the curing time can be further accelerated, or the surface curability at the weir can be enhanced.
添加剤について:
添加剤としては、第一組成物で挙げたものと同様のものが挙げられる。第二組成物に添加する添加剤としては、重合禁止剤、光安定剤が好ましい。特に、重合開始剤より少ない量の重合禁止剤を含ませることによって、第二組成物の貯蔵安定性を改善でき、第二組成物の硬化物の分子量も調整できる。 About additives:
As an additive, the thing similar to what was mentioned by the 1st composition is mentioned. As an additive added to the second composition, a polymerization inhibitor and a light stabilizer are preferable. In particular, the storage stability of the second composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the second composition can also be adjusted.
添加剤としては、第一組成物で挙げたものと同様のものが挙げられる。第二組成物に添加する添加剤としては、重合禁止剤、光安定剤が好ましい。特に、重合開始剤より少ない量の重合禁止剤を含ませることによって、第二組成物の貯蔵安定性を改善でき、第二組成物の硬化物の分子量も調整できる。 About additives:
As an additive, the thing similar to what was mentioned by the 1st composition is mentioned. As an additive added to the second composition, a polymerization inhibitor and a light stabilizer are preferable. In particular, the storage stability of the second composition can be improved by including a smaller amount of the polymerization inhibitor than the polymerization initiator, and the molecular weight of the cured product of the second composition can also be adjusted.
各原料の配合比について:
第二組成物におけるモノマー(G)の割合は、オリゴマー(F)およびモノマー(G)の合計(100質量%)のうち、15~50質量%が好ましく、20~45質量%がより好ましく、25~40質量%がさらに好ましい。モノマー(G)の割合が15質量%以上であれば、第二組成物の硬化性、透明面材と堰との密着性が良好となる。モノマー(G)の割合が50質量%以下であれば、第二組成物の粘度を500Pa・s以上に調整しやすい。 About the mixing ratio of each raw material:
The proportion of the monomer (G) in the second composition is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, out of the total (100% by mass) of the oligomer (F) and the monomer (G), 25 More preferably, it is 40% by mass. When the proportion of the monomer (G) is 15% by mass or more, the curability of the second composition and the adhesion between the transparent surface material and the weir are good. If the ratio of a monomer (G) is 50 mass% or less, it will be easy to adjust the viscosity of a 2nd composition to 500 Pa.s or more.
第二組成物におけるモノマー(G)の割合は、オリゴマー(F)およびモノマー(G)の合計(100質量%)のうち、15~50質量%が好ましく、20~45質量%がより好ましく、25~40質量%がさらに好ましい。モノマー(G)の割合が15質量%以上であれば、第二組成物の硬化性、透明面材と堰との密着性が良好となる。モノマー(G)の割合が50質量%以下であれば、第二組成物の粘度を500Pa・s以上に調整しやすい。 About the mixing ratio of each raw material:
The proportion of the monomer (G) in the second composition is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, out of the total (100% by mass) of the oligomer (F) and the monomer (G), 25 More preferably, it is 40% by mass. When the proportion of the monomer (G) is 15% by mass or more, the curability of the second composition and the adhesion between the transparent surface material and the weir are good. If the ratio of a monomer (G) is 50 mass% or less, it will be easy to adjust the viscosity of a 2nd composition to 500 Pa.s or more.
なお、オリゴマー(F1)の合成において、プレポリマーのイソシアネート基と反応したモノマー(G2)は、オリゴマー(F)の一部として存在するため、モノマー(G)の割合には含めない。一方、オリゴマー(F1)の合成において、希釈剤として用いたモノマー(G1)、およびオリゴマー(F1)を合成した後に添加されたモノマー(G)は、モノマー(G)の割合に含める。
In addition, in the synthesis | combination of an oligomer (F1), since the monomer (G2) reacted with the isocyanate group of a prepolymer exists as a part of oligomer (F), it is not included in the ratio of a monomer (G). On the other hand, in the synthesis of the oligomer (F1), the monomer (G1) used as a diluent and the monomer (G) added after synthesizing the oligomer (F1) are included in the ratio of the monomer (G).
第二組成物における光重合開始剤(E2)の配合量は、オリゴマー(F)およびモノマー(G)の合計100質量部に対して、0.01~10質量部が好ましく、0.1~5質量部がより好ましい。
第二組成物における添加剤の合計量は、オリゴマー(F)およびモノマー(G)の合計100質量部に対して、10質量部以下が好ましく、5質量部以下がより好ましい。 The blending amount of the photopolymerization initiator (E2) in the second composition is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts per 100 parts by mass in total of the oligomer (F) and the monomer (G). Part by mass is more preferable.
The total amount of additives in the second composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the oligomer (F) and the monomer (G).
第二組成物における添加剤の合計量は、オリゴマー(F)およびモノマー(G)の合計100質量部に対して、10質量部以下が好ましく、5質量部以下がより好ましい。 The blending amount of the photopolymerization initiator (E2) in the second composition is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts per 100 parts by mass in total of the oligomer (F) and the monomer (G). Part by mass is more preferable.
The total amount of additives in the second composition is preferably 10 parts by mass or less and more preferably 5 parts by mass or less with respect to 100 parts by mass in total of the oligomer (F) and the monomer (G).
第二組成物の粘度について:
第二組成物の粘度は、500~3000Pa・sが好ましく、800~2500Pa・sがより好ましく、1000~2000Pa・sがさらに好ましい。第二組成物の粘度が500Pa・s以上であれば、硬化前の堰の形状を比較的長時間維持でき、硬化前の堰の高さを充分に維持できる。第二組成物の粘度が3000Pa・s以下であれば、硬化前の堰を塗布によって形成できる。
また、第二組成物の粘度が500Pa・s未満であっても、第二組成物が光硬化性樹脂組成物である場合には、塗布の直後に光を照射することによって、光照射後の第二組成物の粘度を前記好ましい範囲とすればよい。塗布の容易さからは、第二組成物の塗布時の粘度が500Pa・s未満である方が好ましく、200Pa・s以下がさらに好ましい。 Regarding the viscosity of the second composition:
The viscosity of the second composition is preferably 500 to 3000 Pa · s, more preferably 800 to 2500 Pa · s, and still more preferably 1000 to 2000 Pa · s. If the viscosity of the second composition is 500 Pa · s or more, the shape of the weir before curing can be maintained for a relatively long time, and the height of the weir before curing can be sufficiently maintained. If the viscosity of the second composition is 3000 Pa · s or less, the weir before curing can be formed by coating.
In addition, even if the viscosity of the second composition is less than 500 Pa · s, when the second composition is a photocurable resin composition, by irradiating light immediately after coating, What is necessary is just to let the viscosity of a 2nd composition be the said preferable range. From the viewpoint of ease of application, the viscosity at the time of application of the second composition is preferably less than 500 Pa · s, and more preferably 200 Pa · s or less.
第二組成物の粘度は、500~3000Pa・sが好ましく、800~2500Pa・sがより好ましく、1000~2000Pa・sがさらに好ましい。第二組成物の粘度が500Pa・s以上であれば、硬化前の堰の形状を比較的長時間維持でき、硬化前の堰の高さを充分に維持できる。第二組成物の粘度が3000Pa・s以下であれば、硬化前の堰を塗布によって形成できる。
また、第二組成物の粘度が500Pa・s未満であっても、第二組成物が光硬化性樹脂組成物である場合には、塗布の直後に光を照射することによって、光照射後の第二組成物の粘度を前記好ましい範囲とすればよい。塗布の容易さからは、第二組成物の塗布時の粘度が500Pa・s未満である方が好ましく、200Pa・s以下がさらに好ましい。 Regarding the viscosity of the second composition:
The viscosity of the second composition is preferably 500 to 3000 Pa · s, more preferably 800 to 2500 Pa · s, and still more preferably 1000 to 2000 Pa · s. If the viscosity of the second composition is 500 Pa · s or more, the shape of the weir before curing can be maintained for a relatively long time, and the height of the weir before curing can be sufficiently maintained. If the viscosity of the second composition is 3000 Pa · s or less, the weir before curing can be formed by coating.
In addition, even if the viscosity of the second composition is less than 500 Pa · s, when the second composition is a photocurable resin composition, by irradiating light immediately after coating, What is necessary is just to let the viscosity of a 2nd composition be the said preferable range. From the viewpoint of ease of application, the viscosity at the time of application of the second composition is preferably less than 500 Pa · s, and more preferably 200 Pa · s or less.
(保護フィルム)
保護フィルムには、粘着層と強固に密着しないことが求められる。よって、保護フィルムとしては、ポリエチレン、ポリプロピレン、フッ素系樹脂等の、粘着層との密着性の比較的低いフィルムが好ましい。 (Protective film)
The protective film is required not to adhere firmly to the adhesive layer. Therefore, as the protective film, a film having a relatively low adhesion to the adhesive layer, such as polyethylene, polypropylene, and fluorine resin, is preferable.
保護フィルムには、粘着層と強固に密着しないことが求められる。よって、保護フィルムとしては、ポリエチレン、ポリプロピレン、フッ素系樹脂等の、粘着層との密着性の比較的低いフィルムが好ましい。 (Protective film)
The protective film is required not to adhere firmly to the adhesive layer. Therefore, as the protective film, a film having a relatively low adhesion to the adhesive layer, such as polyethylene, polypropylene, and fluorine resin, is preferable.
後述する製造方法において、支持面材に保護フィルムを貼合する場合、保護フィルムには、支持面材に貼合できることが求められる。よって、この場合には、保護フィルムとしては、密着性の比較的低い基材フィルムの片面が粘着面とされた自己粘着性保護フィルムが好ましい。
保護フィルムの粘着面の粘着力は、アクリル板に対する剥離速度300mm/分での180度剥離試験における50mm幅の試験体にて0.01~0.1Nが好ましく、0.02~0.06Nがより好ましい。前記粘着力が前記下限値以上あれば、支持面材への貼合が可能である。前記粘着力が前記上限値以下であれば、支持面材から保護フィルムを剥離させることが容易である。 In the manufacturing method mentioned later, when bonding a protective film to a support surface material, it is calculated | required that a protective film can be bonded to a support surface material. Therefore, in this case, the protective film is preferably a self-adhesive protective film in which one surface of a base film having relatively low adhesion is an adhesive surface.
The adhesive strength of the adhesive surface of the protective film is preferably 0.01 to 0.1 N, preferably 0.02 to 0.06 N in a 50 mm wide test specimen in a 180 degree peel test with a peel rate of 300 mm / min. More preferred. If the said adhesive force is more than the said lower limit, the bonding to a support surface material is possible. If the adhesive strength is not more than the upper limit value, it is easy to peel the protective film from the support surface material.
保護フィルムの粘着面の粘着力は、アクリル板に対する剥離速度300mm/分での180度剥離試験における50mm幅の試験体にて0.01~0.1Nが好ましく、0.02~0.06Nがより好ましい。前記粘着力が前記下限値以上あれば、支持面材への貼合が可能である。前記粘着力が前記上限値以下であれば、支持面材から保護フィルムを剥離させることが容易である。 In the manufacturing method mentioned later, when bonding a protective film to a support surface material, it is calculated | required that a protective film can be bonded to a support surface material. Therefore, in this case, the protective film is preferably a self-adhesive protective film in which one surface of a base film having relatively low adhesion is an adhesive surface.
The adhesive strength of the adhesive surface of the protective film is preferably 0.01 to 0.1 N, preferably 0.02 to 0.06 N in a 50 mm wide test specimen in a 180 degree peel test with a peel rate of 300 mm / min. More preferred. If the said adhesive force is more than the said lower limit, the bonding to a support surface material is possible. If the adhesive strength is not more than the upper limit value, it is easy to peel the protective film from the support surface material.
保護フィルムの厚さは、用いる樹脂により異なるが、ポリエチレン、ポリプロピレン等の比較的柔軟なフィルムを用いる場合には、0.04~0.2mmが好ましく、0.06~0.1mmがより好ましい。保護フィルムの厚さが前記下限値以上であれば、粘着層から保護フィルムを剥離する際に保護フィルムの変形を抑制できる。保護フィルムの厚さが前記上限値以下であれば、剥離時に保護フィルムが撓みやすく、粘着層から保護フィルムを剥離させることが容易になる。
The thickness of the protective film varies depending on the resin used, but when a relatively flexible film such as polyethylene or polypropylene is used, it is preferably 0.04 to 0.2 mm, more preferably 0.06 to 0.1 mm. If the thickness of a protective film is more than the said lower limit, when peeling a protective film from an adhesion layer, a deformation | transformation of a protective film can be suppressed. If the thickness of the protective film is not more than the above upper limit value, the protective film is easily bent at the time of peeling, and the protective film is easily peeled off from the adhesive layer.
[第1の実施形態]
図1は、本発明の粘着層付き透明面材の第1の実施形態を示す断面図である。
粘着層付き透明面材1は、透明面材10と、透明面材10の表面の周縁部に形成された遮光印刷部12(遮光部)と、遮光印刷部12が形成された側の透明面材10の表面に形成された層状の粘着層14と、粘着層14の表面を覆う、剥離可能な保護フィルム16とを有する。
粘着層付き透明面材1から保護フィルム16を剥離した後、粘着層付き透明面材1と表示パネルと貼合することによって、表示装置を製造できる。 [First Embodiment]
FIG. 1 is a cross-sectional view showing a first embodiment of a transparent surface material with an adhesive layer of the present invention.
Thetransparent surface material 1 with an adhesive layer includes a transparent surface material 10, a light shielding printing portion 12 (light shielding portion) formed on the peripheral edge of the surface of the transparent surface material 10, and a transparent surface on the side where the light shielding printing portion 12 is formed. It has a layered adhesive layer 14 formed on the surface of the material 10 and a peelable protective film 16 covering the surface of the adhesive layer 14.
A display apparatus can be manufactured by peeling theprotective film 16 from the transparent surface material 1 with an adhesion layer, and bonding with the transparent surface material 1 with an adhesion layer and a display panel.
図1は、本発明の粘着層付き透明面材の第1の実施形態を示す断面図である。
粘着層付き透明面材1は、透明面材10と、透明面材10の表面の周縁部に形成された遮光印刷部12(遮光部)と、遮光印刷部12が形成された側の透明面材10の表面に形成された層状の粘着層14と、粘着層14の表面を覆う、剥離可能な保護フィルム16とを有する。
粘着層付き透明面材1から保護フィルム16を剥離した後、粘着層付き透明面材1と表示パネルと貼合することによって、表示装置を製造できる。 [First Embodiment]
FIG. 1 is a cross-sectional view showing a first embodiment of a transparent surface material with an adhesive layer of the present invention.
The
A display apparatus can be manufactured by peeling the
(透明面材)
透明面材10は、後述する表示パネルの画像表示面側(すなわち、視認側)に設けられて表示パネルを保護する。 (Transparent surface material)
Thetransparent surface material 10 is provided on the image display surface side (that is, the viewing side) of the display panel described later to protect the display panel.
透明面材10は、後述する表示パネルの画像表示面側(すなわち、視認側)に設けられて表示パネルを保護する。 (Transparent surface material)
The
透明面材10には、表示画像のコントラストを高めるために、粘着層14が形成された側に対して反対側の表面に反射防止層を設けてもよい。また、目的に応じて、透明面材10の一部または全体を着色したり、透明面材10の表面の一部または全体を磨りガラス状にして光を散乱させたり、透明面材10の表面の一部または全体に微細な凹凸等を形成して透過光を屈折または反射させたりしてもよい。また、着色フィルム、光散乱フィルム、光屈折フィルム、光反射フィルム等を、透明面材10の表面の一部または全体に貼合してもよい。
In order to increase the contrast of the display image, the transparent face material 10 may be provided with an antireflection layer on the surface opposite to the side on which the adhesive layer 14 is formed. Further, depending on the purpose, a part or the whole of the transparent face material 10 is colored, or a part or the whole of the surface of the transparent face material 10 is polished to form a glass to scatter light, or the surface of the transparent face material 10 is scattered. Further, a minute unevenness or the like may be formed on a part or the whole of the light to refract or reflect the transmitted light. Further, a colored film, a light scattering film, a photorefractive film, a light reflecting film, or the like may be bonded to a part or the whole of the surface of the transparent surface material 10.
透明面材10の形状は、表示装置の外形に合わせる意味で、矩形であることが好ましい。表示装置の外形によっては、表示パネルの表示面の全面を覆う、外形形状に曲線を含む形状の透明面材を用いることもできる。
透明面材10の大きさは、表示装置の外形に合わせて適宜設定すればよい、透明面材10の厚さは、機械的強度、透明性の点から、ガラス板の場合は0.5~25mmであることが好ましい。屋内で使用するテレビ受像機、PC用ディスプレイ等の用途では、表示装置の軽量化の点から、1~6mmが好ましく、屋外に設置する公衆表示用途では、3~20mmが好ましい。化学強化ガラスを用いる場合は、ガラス板の厚さは、強度の点で、0.5~1.5mm程度が好ましい。透明樹脂板の場合は、2~10mmが好ましい。 The shape of thetransparent surface material 10 is preferably rectangular in order to match the outer shape of the display device. Depending on the outer shape of the display device, it is possible to use a transparent surface material that covers the entire display surface of the display panel and has a shape that includes a curve in the outer shape.
The size of thetransparent face material 10 may be appropriately set according to the outer shape of the display device. The thickness of the transparent face material 10 is 0.5 to 0.5 in the case of a glass plate from the viewpoint of mechanical strength and transparency. It is preferably 25 mm. For applications such as television receivers and PC displays used indoors, 1 to 6 mm is preferable from the viewpoint of reducing the weight of the display device, and for public display applications installed outdoors, 3 to 20 mm is preferable. When chemically strengthened glass is used, the thickness of the glass plate is preferably about 0.5 to 1.5 mm in terms of strength. In the case of a transparent resin plate, 2 to 10 mm is preferable.
透明面材10の大きさは、表示装置の外形に合わせて適宜設定すればよい、透明面材10の厚さは、機械的強度、透明性の点から、ガラス板の場合は0.5~25mmであることが好ましい。屋内で使用するテレビ受像機、PC用ディスプレイ等の用途では、表示装置の軽量化の点から、1~6mmが好ましく、屋外に設置する公衆表示用途では、3~20mmが好ましい。化学強化ガラスを用いる場合は、ガラス板の厚さは、強度の点で、0.5~1.5mm程度が好ましい。透明樹脂板の場合は、2~10mmが好ましい。 The shape of the
The size of the
(遮光印刷部)
遮光印刷部12は、後述する表示パネルの画像表示領域以外が透明面材10側から視認できないようにして、表示パネルに接続されている配線部材等を隠蔽する。遮光印刷部12は、粘着層14が形成される側またはその反対側の表面に形成することができる。遮光印刷部12と画像表示領域との視差を低減する点では、粘着層14が形成される側の表面に形成することが好ましい。透明面材10がガラス板の場合、遮光印刷部12に黒色顔料を含むセラミック印刷を用いると遮光性が高く好ましい。
表示パネルの配線部材等が、表示パネルを観察する側からは視認できない構造であったり、表示装置の筺体などの他の部材により隠蔽される場合、または、表示パネル以外の被貼合体と粘着層付き透明面材1とを貼合する場合には、遮光印刷部12を透明面材10に形成しない場合もある。 (Shading printing part)
The light-shieldingprinting unit 12 hides wiring members and the like connected to the display panel so that areas other than the image display area of the display panel, which will be described later, are not visible from the transparent surface material 10 side. The light-shielding printing unit 12 can be formed on the surface on which the adhesive layer 14 is formed or on the opposite surface. In terms of reducing the parallax between the light-shielding printing unit 12 and the image display area, it is preferable to form the surface on the side where the adhesive layer 14 is formed. When the transparent surface material 10 is a glass plate, it is preferable to use ceramic printing containing a black pigment for the light shielding printing portion 12 because of high light shielding properties.
When the display panel wiring member or the like has a structure that cannot be seen from the side of the display panel observation, or is concealed by another member such as a housing of the display device, or a bonded object and an adhesive layer other than the display panel In the case of pasting the attachedtransparent face material 1, the light shielding printing portion 12 may not be formed on the transparent face material 10.
遮光印刷部12は、後述する表示パネルの画像表示領域以外が透明面材10側から視認できないようにして、表示パネルに接続されている配線部材等を隠蔽する。遮光印刷部12は、粘着層14が形成される側またはその反対側の表面に形成することができる。遮光印刷部12と画像表示領域との視差を低減する点では、粘着層14が形成される側の表面に形成することが好ましい。透明面材10がガラス板の場合、遮光印刷部12に黒色顔料を含むセラミック印刷を用いると遮光性が高く好ましい。
表示パネルの配線部材等が、表示パネルを観察する側からは視認できない構造であったり、表示装置の筺体などの他の部材により隠蔽される場合、または、表示パネル以外の被貼合体と粘着層付き透明面材1とを貼合する場合には、遮光印刷部12を透明面材10に形成しない場合もある。 (Shading printing part)
The light-shielding
When the display panel wiring member or the like has a structure that cannot be seen from the side of the display panel observation, or is concealed by another member such as a housing of the display device, or a bonded object and an adhesive layer other than the display panel In the case of pasting the attached
(粘着層)
粘着層14は、上述した第一組成物を硬化してなる透明樹脂からなる層である。 (Adhesive layer)
Theadhesive layer 14 is a layer made of a transparent resin formed by curing the first composition described above.
粘着層14は、上述した第一組成物を硬化してなる透明樹脂からなる層である。 (Adhesive layer)
The
(保護フィルム)
保護フィルム16としては、上述したポリエチレン、ポリプロピレン、フッ素系樹脂等の粘着層との密着性の比較的低いフィルムが用いられる。 (Protective film)
As theprotective film 16, a film having a relatively low adhesiveness to the adhesive layer such as the above-described polyethylene, polypropylene, and fluorine resin is used.
保護フィルム16としては、上述したポリエチレン、ポリプロピレン、フッ素系樹脂等の粘着層との密着性の比較的低いフィルムが用いられる。 (Protective film)
As the
[第2の実施形態]
図2は、本発明の粘着層付き透明面材の第2の実施形態を示す断面図である。
粘着層付き透明面材2は、透明面材10と、透明面材10の表面の周縁部に形成された遮光印刷部12(遮光部)と、遮光印刷部12が形成された側の透明面材10の表面に形成された層状の粘着層14と、粘着層14の周縁に接した状態で粘着層14を囲む枠状の堰15と、粘着層14の表面を覆う、剥離可能な保護フィルム16とを有する。
粘着層付き透明面材2から保護フィルム16を剥離した後、粘着層付き透明面材2と表示パネルと貼合することによって、表示装置を製造できる。
第1の実施形態と同じ構成については、同じ符号を付して説明を省略する。 [Second Embodiment]
FIG. 2 is a cross-sectional view showing a second embodiment of the transparent surface material with an adhesive layer of the present invention.
Thetransparent surface material 2 with the adhesive layer includes a transparent surface material 10, a light shielding printing portion 12 (light shielding portion) formed on the peripheral edge of the surface of the transparent surface material 10, and a transparent surface on the side where the light shielding printing portion 12 is formed. A layered adhesive layer 14 formed on the surface of the material 10, a frame-like weir 15 surrounding the adhesive layer 14 in contact with the periphery of the adhesive layer 14, and a peelable protective film covering the surface of the adhesive layer 14 16.
After peeling off theprotective film 16 from the transparent surface material 2 with the adhesive layer, the display device can be produced by pasting the transparent surface material 2 with the adhesive layer and the display panel.
About the same structure as 1st Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.
図2は、本発明の粘着層付き透明面材の第2の実施形態を示す断面図である。
粘着層付き透明面材2は、透明面材10と、透明面材10の表面の周縁部に形成された遮光印刷部12(遮光部)と、遮光印刷部12が形成された側の透明面材10の表面に形成された層状の粘着層14と、粘着層14の周縁に接した状態で粘着層14を囲む枠状の堰15と、粘着層14の表面を覆う、剥離可能な保護フィルム16とを有する。
粘着層付き透明面材2から保護フィルム16を剥離した後、粘着層付き透明面材2と表示パネルと貼合することによって、表示装置を製造できる。
第1の実施形態と同じ構成については、同じ符号を付して説明を省略する。 [Second Embodiment]
FIG. 2 is a cross-sectional view showing a second embodiment of the transparent surface material with an adhesive layer of the present invention.
The
After peeling off the
About the same structure as 1st Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.
(堰)
堰15は、上述した第二組成物を硬化してなる透明樹脂からなる部分である。 (Weir)
Theweir 15 is a portion made of a transparent resin obtained by curing the above-described second composition.
堰15は、上述した第二組成物を硬化してなる透明樹脂からなる部分である。 (Weir)
The
(他の実施形態)
本発明の粘着層付き透明面材は、透明面材と粘着層とを有し、粘着層中の水酸基の濃度およびウレタン結合の濃度が特定の範囲内であるものであればよく、図示例のものに限定はされない。 (Other embodiments)
The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer, and the hydroxyl group concentration and the urethane bond concentration in the adhesive layer may be within a specific range. The thing is not limited.
本発明の粘着層付き透明面材は、透明面材と粘着層とを有し、粘着層中の水酸基の濃度およびウレタン結合の濃度が特定の範囲内であるものであればよく、図示例のものに限定はされない。 (Other embodiments)
The transparent surface material with an adhesive layer of the present invention has a transparent surface material and an adhesive layer, and the hydroxyl group concentration and the urethane bond concentration in the adhesive layer may be within a specific range. The thing is not limited.
(作用機序)
以上説明した本発明の粘着層付き透明面材にあっては、粘着層中の水酸基の濃度が、600×10-6モル/g以下であり、粘着層中のウレタン結合の濃度が、150×10-6モル/g以下であるため、被貼合物(表示パネル等)と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。また、粘着層中の水酸基の濃度が、100×10-6モル/g以上であるため、粘着層と透明面材との密着性、および粘着層と被貼合物との密着性が良好となる。 (Mechanism of action)
In the transparent surface material with an adhesive layer of the present invention described above, the concentration of hydroxyl groups in the adhesive layer is 600 × 10 −6 mol / g or less, and the concentration of urethane bonds in the adhesive layer is 150 × Since it is 10 −6 mol / g or less, the bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive layer can rapidly disappear when it is bonded to the object to be bonded (display panel or the like). Further, since the concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded are good. Become.
以上説明した本発明の粘着層付き透明面材にあっては、粘着層中の水酸基の濃度が、600×10-6モル/g以下であり、粘着層中のウレタン結合の濃度が、150×10-6モル/g以下であるため、被貼合物(表示パネル等)と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る。また、粘着層中の水酸基の濃度が、100×10-6モル/g以上であるため、粘着層と透明面材との密着性、および粘着層と被貼合物との密着性が良好となる。 (Mechanism of action)
In the transparent surface material with an adhesive layer of the present invention described above, the concentration of hydroxyl groups in the adhesive layer is 600 × 10 −6 mol / g or less, and the concentration of urethane bonds in the adhesive layer is 150 × Since it is 10 −6 mol / g or less, the bubbles remaining at the interface between the object to be bonded and the pressure-sensitive adhesive layer can rapidly disappear when it is bonded to the object to be bonded (display panel or the like). Further, since the concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 mol / g or more, the adhesiveness between the adhesive layer and the transparent surface material and the adhesiveness between the adhesive layer and the object to be bonded are good. Become.
<粘着層付き透明面材の製造方法>
本発明の粘着層付き透明面材の製造方法は、下記工程(α)、下記工程(β)および下記工程(γ)を有する。下記工程(α)、下記工程(β)および下記工程(γ)の順としては、この順が好ましい。
(α)透明面材の表面に液状の硬化性樹脂組成物を供給し、必要に応じて硬化性樹脂組成物を部分的に硬化させて部分硬化物とする工程。
(β)必要に応じて、硬化性樹脂組成物または部分硬化物の表面を保護フィルムで覆う工程。
(γ)硬化性樹脂組成物または部分硬化物を硬化させて、粘着層を形成する工程。 <Method for producing transparent surface material with adhesive layer>
The manufacturing method of the transparent surface material with the adhesion layer of this invention has the following process ((alpha)), the following process ((beta)), and the following process ((gamma)). This order is preferable as the order of the following process (α), the following process (β), and the following process (γ).
(Α) A step of supplying a liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
(Β) A step of covering the surface of the curable resin composition or the partially cured product with a protective film as necessary.
(Γ) A step of curing the curable resin composition or the partially cured product to form an adhesive layer.
本発明の粘着層付き透明面材の製造方法は、下記工程(α)、下記工程(β)および下記工程(γ)を有する。下記工程(α)、下記工程(β)および下記工程(γ)の順としては、この順が好ましい。
(α)透明面材の表面に液状の硬化性樹脂組成物を供給し、必要に応じて硬化性樹脂組成物を部分的に硬化させて部分硬化物とする工程。
(β)必要に応じて、硬化性樹脂組成物または部分硬化物の表面を保護フィルムで覆う工程。
(γ)硬化性樹脂組成物または部分硬化物を硬化させて、粘着層を形成する工程。 <Method for producing transparent surface material with adhesive layer>
The manufacturing method of the transparent surface material with the adhesion layer of this invention has the following process ((alpha)), the following process ((beta)), and the following process ((gamma)). This order is preferable as the order of the following process (α), the following process (β), and the following process (γ).
(Α) A step of supplying a liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
(Β) A step of covering the surface of the curable resin composition or the partially cured product with a protective film as necessary.
(Γ) A step of curing the curable resin composition or the partially cured product to form an adhesive layer.
本発明の粘着層付き透明面材の製造方法は、堰を有しない粘着層付き透明面材(たとえば第1の実施形態の粘着層付き透明面材)の製造方法と、堰を有する粘着層付き透明面材(たとえば第2の実施形態の粘着層付き透明面材)の製造方法とに分けられる。
The method for producing a transparent surface material with an adhesive layer of the present invention includes a method for producing a transparent surface material with an adhesive layer not having a weir (for example, the transparent surface material with an adhesive layer of the first embodiment), and an adhesive layer having a weir. It is divided into the manufacturing method of a transparent surface material (for example, the transparent surface material with the adhesion layer of 2nd Embodiment).
[堰を有しない粘着層付き透明面材の製造方法]
堰を有しない粘着層付き透明面材の製造方法としては、たとえば、下記工程(α1)、下記工程(β1)および下記工程(γ1)を有する方法が挙げられる。
(α1)透明面材の表面に液状の粘着層形成用硬化性樹脂組成物を層状に供給し、透明面材の表面に供給された粘着層形成用硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(β1)必要に応じて、部分硬化物の層の表面を保護フィルムで覆う工程。
(γ1)部分硬化物の層をさらに硬化させて、粘着層を形成する工程。 [Method for producing transparent surface material with adhesive layer having no weir]
As a manufacturing method of the transparent surface material with the adhesion layer which does not have a weir, the method which has the following process ((alpha) 1), the following process ((beta) 1), and the following process ((gamma) 1) is mentioned, for example.
(Α1) A liquid adhesive layer-forming curable resin composition is supplied to the surface of the transparent surface material in a layered manner, and the adhesive layer-forming curable resin composition supplied to the surface of the transparent surface material is partially cured. Forming a layer of partially cured product.
(Β1) A step of covering the surface of the partially cured product layer with a protective film as necessary.
(Γ1) A step of further curing the partially cured product layer to form an adhesive layer.
堰を有しない粘着層付き透明面材の製造方法としては、たとえば、下記工程(α1)、下記工程(β1)および下記工程(γ1)を有する方法が挙げられる。
(α1)透明面材の表面に液状の粘着層形成用硬化性樹脂組成物を層状に供給し、透明面材の表面に供給された粘着層形成用硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(β1)必要に応じて、部分硬化物の層の表面を保護フィルムで覆う工程。
(γ1)部分硬化物の層をさらに硬化させて、粘着層を形成する工程。 [Method for producing transparent surface material with adhesive layer having no weir]
As a manufacturing method of the transparent surface material with the adhesion layer which does not have a weir, the method which has the following process ((alpha) 1), the following process ((beta) 1), and the following process ((gamma) 1) is mentioned, for example.
(Α1) A liquid adhesive layer-forming curable resin composition is supplied to the surface of the transparent surface material in a layered manner, and the adhesive layer-forming curable resin composition supplied to the surface of the transparent surface material is partially cured. Forming a layer of partially cured product.
(Β1) A step of covering the surface of the partially cured product layer with a protective film as necessary.
(Γ1) A step of further curing the partially cured product layer to form an adhesive layer.
(工程(α1))
工程(α1)は、下記の工程(α1a)であってもよく、下記の工程(α1b)であってもよい。粘着層形成用硬化性樹脂組成物の供給、硬化に必要な装置を設置する面積が少なく済む点、および透明面材の表面に供給された粘着層形成用硬化性樹脂組成物の周縁部が外方へ拡がって周縁部が薄肉化することが抑えられる点から、工程(α1a)が好ましい。 (Process (α1))
The step (α1) may be the following step (α1a) or the following step (α1b). Supply of the adhesive layer-forming curable resin composition, a small area for installing a device necessary for curing, and the periphery of the adhesive layer-forming curable resin composition supplied to the surface of the transparent surface The step (α1a) is preferable from the viewpoint that the peripheral portion can be prevented from being thinned by spreading outward.
工程(α1)は、下記の工程(α1a)であってもよく、下記の工程(α1b)であってもよい。粘着層形成用硬化性樹脂組成物の供給、硬化に必要な装置を設置する面積が少なく済む点、および透明面材の表面に供給された粘着層形成用硬化性樹脂組成物の周縁部が外方へ拡がって周縁部が薄肉化することが抑えられる点から、工程(α1a)が好ましい。 (Process (α1))
The step (α1) may be the following step (α1a) or the following step (α1b). Supply of the adhesive layer-forming curable resin composition, a small area for installing a device necessary for curing, and the periphery of the adhesive layer-forming curable resin composition supplied to the surface of the transparent surface The step (α1a) is preferable from the viewpoint that the peripheral portion can be prevented from being thinned by spreading outward.
(α1a)透明面材の表面に液状の粘着層形成用硬化性樹脂組成物を層状に供給しながら、透明面材の表面に供給された粘着層形成用硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(α1b)透明面材の表面に液状の粘着層形成用硬化性樹脂組成物を層状に供給し、粘着層形成用硬化性樹脂組成物の層を形成した後、粘着層形成用硬化性樹脂組成物の層を部分的に硬化させて部分硬化物の層を形成する工程。 (Α1a) Partially curing the curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material while supplying the liquid curable resin composition for forming an adhesive layer to the surface of the transparent surface material And a step of forming a partially cured product layer.
(Α1b) A liquid adhesive layer-forming curable resin composition is supplied to the surface of the transparent surface material in layers, and after forming the adhesive layer-forming curable resin composition, the adhesive layer-forming curable resin composition A step of partially curing the layer of the product to form a layer of the partially cured product.
(α1b)透明面材の表面に液状の粘着層形成用硬化性樹脂組成物を層状に供給し、粘着層形成用硬化性樹脂組成物の層を形成した後、粘着層形成用硬化性樹脂組成物の層を部分的に硬化させて部分硬化物の層を形成する工程。 (Α1a) Partially curing the curable resin composition for forming an adhesive layer supplied to the surface of the transparent surface material while supplying the liquid curable resin composition for forming an adhesive layer to the surface of the transparent surface material And a step of forming a partially cured product layer.
(Α1b) A liquid adhesive layer-forming curable resin composition is supplied to the surface of the transparent surface material in layers, and after forming the adhesive layer-forming curable resin composition, the adhesive layer-forming curable resin composition A step of partially curing the layer of the product to form a layer of the partially cured product.
粘着層形成用硬化性樹脂組成物の供給は、ダイコータ、ナイフコータ等を用いて行われる。
The supply of the curable resin composition for forming an adhesive layer is performed using a die coater, a knife coater or the like.
粘着層形成用硬化性樹脂組成物の硬化は、光硬化性樹脂組成物の場合、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射することによって行われる。光照射は、空気中で行ってもよく、窒素ガス供給下で行ってもよい。光照射は、粘着層形成用硬化性樹脂組成物を供給した側から行うことが好ましい。
粘着層形成用硬化性樹脂組成物の硬化は、熱硬化性樹脂組成物の場合、加熱によって行われる。 In the case of a photocurable resin composition, the curable resin composition for forming an adhesive layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED). . Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the side where the curable resin composition for forming an adhesive layer is supplied.
In the case of a thermosetting resin composition, curing of the adhesive layer forming curable resin composition is performed by heating.
粘着層形成用硬化性樹脂組成物の硬化は、熱硬化性樹脂組成物の場合、加熱によって行われる。 In the case of a photocurable resin composition, the curable resin composition for forming an adhesive layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED). . Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the side where the curable resin composition for forming an adhesive layer is supplied.
In the case of a thermosetting resin composition, curing of the adhesive layer forming curable resin composition is performed by heating.
部分硬化物の層の35℃における貯蔵せん断弾性率は、目標とする粘着層の35℃における貯蔵せん断弾性率の1/200~1/5である。部分硬化物の層の35℃における貯蔵せん断弾性率が前記下限以上であれば、保護フィルムを重ねる際に部分硬化物の層の形状が崩れない。部分硬化物の層の35℃における貯蔵せん断弾性率が前記上限以下であれば、保護フィルムとの密着力が充分に高くなる。
The storage shear modulus at 35 ° C. of the partially cured product layer is 1/200 to 1/5 of the storage shear modulus at 35 ° C. of the target adhesive layer. If the storage shear modulus at 35 ° C. of the partially cured product layer is equal to or higher than the lower limit, the shape of the partially cured product layer does not collapse when the protective film is stacked. If the storage shear modulus at 35 ° C. of the partially cured product layer is less than or equal to the above upper limit, the adhesion with the protective film will be sufficiently high.
(工程(β1))
工程(β1)においては、部分硬化物の層の表面に保護フィルムを重ねて、部分硬化物の層の表面を保護フィルムで覆う。
重ね合わせは、大気圧下で行ってもよく、後述する工程(β2)のように減圧雰囲気下で行ってもよい。
重ね合わせた後、部分硬化物の層の形状が崩れないように、部分硬化物の層の端から徐々に圧着することが好ましい。圧着には、ラミネータを用いてもよい。 (Process (β1))
In the step (β1), a protective film is overlaid on the surface of the partially cured product layer, and the surface of the partially cured product layer is covered with the protective film.
The superposition may be performed under atmospheric pressure, or may be performed under a reduced-pressure atmosphere as in the step (β2) described later.
After the overlapping, it is preferable to gradually press-bond from the end of the partially cured product layer so that the shape of the partially cured product layer does not collapse. A laminator may be used for the pressure bonding.
工程(β1)においては、部分硬化物の層の表面に保護フィルムを重ねて、部分硬化物の層の表面を保護フィルムで覆う。
重ね合わせは、大気圧下で行ってもよく、後述する工程(β2)のように減圧雰囲気下で行ってもよい。
重ね合わせた後、部分硬化物の層の形状が崩れないように、部分硬化物の層の端から徐々に圧着することが好ましい。圧着には、ラミネータを用いてもよい。 (Process (β1))
In the step (β1), a protective film is overlaid on the surface of the partially cured product layer, and the surface of the partially cured product layer is covered with the protective film.
The superposition may be performed under atmospheric pressure, or may be performed under a reduced-pressure atmosphere as in the step (β2) described later.
After the overlapping, it is preferable to gradually press-bond from the end of the partially cured product layer so that the shape of the partially cured product layer does not collapse. A laminator may be used for the pressure bonding.
(工程(γ1))
工程(γ1)においては、部分硬化物の層をさらに硬化させて、粘着層を形成する。
部分硬化物の層の硬化は、光硬化性樹脂組成物の場合、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射することによって行われる。光照射は、空気中で行ってもよく、窒素ガス供給下で行ってもよい。光照射は、保護フィルム側から行うことが好ましい。
部分硬化物の層の硬化は、熱硬化性樹脂組成物の場合、加熱によって行われる。 (Process (γ1))
In the step (γ1), the partially cured product layer is further cured to form an adhesive layer.
In the case of a photocurable resin composition, the partially cured product layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED). Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the protective film side.
In the case of a thermosetting resin composition, the partially cured product layer is cured by heating.
工程(γ1)においては、部分硬化物の層をさらに硬化させて、粘着層を形成する。
部分硬化物の層の硬化は、光硬化性樹脂組成物の場合、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射することによって行われる。光照射は、空気中で行ってもよく、窒素ガス供給下で行ってもよい。光照射は、保護フィルム側から行うことが好ましい。
部分硬化物の層の硬化は、熱硬化性樹脂組成物の場合、加熱によって行われる。 (Process (γ1))
In the step (γ1), the partially cured product layer is further cured to form an adhesive layer.
In the case of a photocurable resin composition, the partially cured product layer is cured by irradiating ultraviolet rays or short-wavelength visible light from a light source (such as an ultraviolet lamp, a high-pressure mercury lamp, or a UV-LED). Light irradiation may be performed in air or may be performed under supply of nitrogen gas. The light irradiation is preferably performed from the protective film side.
In the case of a thermosetting resin composition, the partially cured product layer is cured by heating.
[第1の実施形態の粘着層付き透明面材の製造方法]
以下、第1の実施形態の粘着層付き透明面材1の製造方法の一例を、図面を用いて具体的に説明する。 [Method for Producing Transparent Surface Material with Adhesive Layer of First Embodiment]
Hereinafter, an example of the manufacturing method of thetransparent surface material 1 with the adhesion layer of 1st Embodiment is demonstrated concretely using drawing.
以下、第1の実施形態の粘着層付き透明面材1の製造方法の一例を、図面を用いて具体的に説明する。 [Method for Producing Transparent Surface Material with Adhesive Layer of First Embodiment]
Hereinafter, an example of the manufacturing method of the
(工程(α1))
工程(α1)においては、図3および図4に示すように、搬送装置(図示略)上に載置された透明面材10を図中矢印の方向に一定速度で移動させながら、透明面材10の移動方向に直交する方向にスリット(図示略)が延びるように配置されたダイコータ62から、透明面材10の表面に液状の第一組成物18を線状に吐出する。この際、線状の第一組成物18の両端が、遮光印刷部12上に位置するようにする。透明面材10の移動とともに、透明面材10の透光部の全面および遮光印刷部12の内縁側を覆うように、第一組成物18が層状に供給される。 (Process (α1))
In the step (α1), as shown in FIGS. 3 and 4, thetransparent surface material 10 placed on the transport device (not shown) is moved at a constant speed in the direction of the arrow in the drawing, The liquid first composition 18 is linearly discharged onto the surface of the transparent face material 10 from a die coater 62 arranged so that a slit (not shown) extends in a direction perpendicular to the moving direction of the material 10. At this time, both ends of the linear first composition 18 are positioned on the light-shielding printing unit 12. Along with the movement of the transparent face material 10, the first composition 18 is supplied in layers so as to cover the entire light-transmitting portion of the transparent face material 10 and the inner edge side of the light-shielding print portion 12.
工程(α1)においては、図3および図4に示すように、搬送装置(図示略)上に載置された透明面材10を図中矢印の方向に一定速度で移動させながら、透明面材10の移動方向に直交する方向にスリット(図示略)が延びるように配置されたダイコータ62から、透明面材10の表面に液状の第一組成物18を線状に吐出する。この際、線状の第一組成物18の両端が、遮光印刷部12上に位置するようにする。透明面材10の移動とともに、透明面材10の透光部の全面および遮光印刷部12の内縁側を覆うように、第一組成物18が層状に供給される。 (Process (α1))
In the step (α1), as shown in FIGS. 3 and 4, the
第一組成物18を層状に供給しながら、ダイコータ62に対して透明面材10の移動方向の下流側に、長手方向が透明面材10の移動方向に直交するように配置されたライン状のLED光源64から、線状の光(紫外線や短波長の可視光)を照射し、透明面材10の表面に供給された第一組成物18を硬化させて部分硬化物の層20を形成する。
While supplying the first composition 18 in a layered manner, a line-like shape is arranged downstream of the die coater 62 in the moving direction of the transparent face material 10 so that the longitudinal direction is orthogonal to the moving direction of the transparent face material 10. The LED light source 64 is irradiated with linear light (ultraviolet light or short-wavelength visible light), and the first composition 18 supplied to the surface of the transparent surface material 10 is cured to form the partially cured material layer 20. .
(工程(β1))
工程(β1)においては、図5に示すように、大気圧下で部分硬化物の層20の表面に保護フィルム16を重ね、ラミネータ(図示略)を用いて部分硬化物の層20の端から徐々に保護フィルム16を圧着して、部分硬化物の層20の表面を保護フィルム16で覆う。 (Process (β1))
In the step (β1), as shown in FIG. 5, theprotective film 16 is placed on the surface of the partially cured product layer 20 under atmospheric pressure, and from the end of the partially cured product layer 20 using a laminator (not shown). The protective film 16 is gradually pressure-bonded to cover the surface of the partially cured product layer 20 with the protective film 16.
工程(β1)においては、図5に示すように、大気圧下で部分硬化物の層20の表面に保護フィルム16を重ね、ラミネータ(図示略)を用いて部分硬化物の層20の端から徐々に保護フィルム16を圧着して、部分硬化物の層20の表面を保護フィルム16で覆う。 (Process (β1))
In the step (β1), as shown in FIG. 5, the
(工程(γ1))
工程(γ1)においては、保護フィルム16側から部分硬化物の層20に光(紫外線や短波長の可視光)を照射し、部分硬化物の層20をさらに硬化させて粘着層14を形成することによって、図1に示す粘着層付き透明面材1が得られる。 (Process (γ1))
In the step (γ1), the partially curedproduct layer 20 is irradiated with light (ultraviolet rays or short-wavelength visible light) from the protective film 16 side, and the partially cured product layer 20 is further cured to form the adhesive layer 14. Thereby, the transparent surface material 1 with the adhesion layer shown in FIG. 1 is obtained.
工程(γ1)においては、保護フィルム16側から部分硬化物の層20に光(紫外線や短波長の可視光)を照射し、部分硬化物の層20をさらに硬化させて粘着層14を形成することによって、図1に示す粘着層付き透明面材1が得られる。 (Process (γ1))
In the step (γ1), the partially cured
[堰を有する粘着層付き透明面材の製造方法]
堰を有する粘着層付き透明面材の製造方法としては、たとえば、下記工程(α21)、下記工程(α22)、下記工程(β2)、下記工程(γ21)および下記工程(γ22)を有する方法が挙げられる。
(α21)透明面材の表面の周縁部に枠状の堰を形成する工程。
(α22)堰で囲まれた領域に粘着層形成用硬化性樹脂組成物を供給する工程。
(β2)減圧雰囲気下にて、粘着層形成用硬化性樹脂組成物の層の上に、保護フィルム付き支持面材を、保護フィルムが粘着層形成用硬化性樹脂組成物の層の表面に接するように重ねて、透明面材、保護フィルムおよび堰で粘着層形成用硬化性樹脂組成物の層が密封された積層体を得る工程。
(γ21)工程(β2)より高い圧力雰囲気下に積層体を置いた状態にて、粘着層形成用硬化性樹脂組成物の層を硬化させて、粘着層を形成する工程。
(γ22)工程(γ21)の後、支持面材を保護フィルムから剥離する工程。 [Method for producing transparent surface material with adhesive layer having weir]
As a manufacturing method of the transparent surface material with an adhesive layer having a weir, for example, a method having the following step (α21), the following step (α22), the following step (β2), the following step (γ21), and the following step (γ22). Can be mentioned.
(Α21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
(Α22) A step of supplying the adhesive layer-forming curable resin composition to the region surrounded by the weir.
(Β2) A support surface material with a protective film is placed on the layer of the curable resin composition for forming an adhesive layer under a reduced pressure atmosphere, and the protective film is in contact with the surface of the layer of the curable resin composition for forming an adhesive layer. The process of obtaining the laminated body on which the layer of the curable resin composition for adhesion layer formation was sealed with the transparent surface material, the protective film, and the weir.
(Γ21) A step of forming an adhesive layer by curing the layer of the curable resin composition for forming an adhesive layer in a state where the laminate is placed under a higher pressure atmosphere than the step (β2).
(Γ22) A step of peeling the support surface material from the protective film after the step (γ21).
堰を有する粘着層付き透明面材の製造方法としては、たとえば、下記工程(α21)、下記工程(α22)、下記工程(β2)、下記工程(γ21)および下記工程(γ22)を有する方法が挙げられる。
(α21)透明面材の表面の周縁部に枠状の堰を形成する工程。
(α22)堰で囲まれた領域に粘着層形成用硬化性樹脂組成物を供給する工程。
(β2)減圧雰囲気下にて、粘着層形成用硬化性樹脂組成物の層の上に、保護フィルム付き支持面材を、保護フィルムが粘着層形成用硬化性樹脂組成物の層の表面に接するように重ねて、透明面材、保護フィルムおよび堰で粘着層形成用硬化性樹脂組成物の層が密封された積層体を得る工程。
(γ21)工程(β2)より高い圧力雰囲気下に積層体を置いた状態にて、粘着層形成用硬化性樹脂組成物の層を硬化させて、粘着層を形成する工程。
(γ22)工程(γ21)の後、支持面材を保護フィルムから剥離する工程。 [Method for producing transparent surface material with adhesive layer having weir]
As a manufacturing method of the transparent surface material with an adhesive layer having a weir, for example, a method having the following step (α21), the following step (α22), the following step (β2), the following step (γ21), and the following step (γ22). Can be mentioned.
(Α21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
(Α22) A step of supplying the adhesive layer-forming curable resin composition to the region surrounded by the weir.
(Β2) A support surface material with a protective film is placed on the layer of the curable resin composition for forming an adhesive layer under a reduced pressure atmosphere, and the protective film is in contact with the surface of the layer of the curable resin composition for forming an adhesive layer. The process of obtaining the laminated body on which the layer of the curable resin composition for adhesion layer formation was sealed with the transparent surface material, the protective film, and the weir.
(Γ21) A step of forming an adhesive layer by curing the layer of the curable resin composition for forming an adhesive layer in a state where the laminate is placed under a higher pressure atmosphere than the step (β2).
(Γ22) A step of peeling the support surface material from the protective film after the step (γ21).
(工程(α21))
まず、工程(α21)として、透明面材の表面の周縁部に、液状の堰形成用硬化性樹脂組成物を塗布して堰を形成する。
塗布は、印刷機、ディスペンサ等を用いて行われる。堰は、未硬化の状態であってもよく、部分的に硬化させた半硬化の状態であってもよい。堰の部分硬化は、堰形成用硬化性樹脂組成物が光硬化性組成物である場合、光の照射によって行う。たとえば、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射して、光硬化性樹脂組成物を部分硬化させる。 (Process (α21))
First, as a step (α21), a liquid weir-forming curable resin composition is applied to the periphery of the surface of the transparent face material to form a weir.
The application is performed using a printing machine, a dispenser, or the like. The weir may be in an uncured state or a partially cured semi-cured state. When the curable resin composition for weir formation is a photocurable composition, partial curing of the weir is performed by light irradiation. For example, the photocurable resin composition is partially cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.).
まず、工程(α21)として、透明面材の表面の周縁部に、液状の堰形成用硬化性樹脂組成物を塗布して堰を形成する。
塗布は、印刷機、ディスペンサ等を用いて行われる。堰は、未硬化の状態であってもよく、部分的に硬化させた半硬化の状態であってもよい。堰の部分硬化は、堰形成用硬化性樹脂組成物が光硬化性組成物である場合、光の照射によって行う。たとえば、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射して、光硬化性樹脂組成物を部分硬化させる。 (Process (α21))
First, as a step (α21), a liquid weir-forming curable resin composition is applied to the periphery of the surface of the transparent face material to form a weir.
The application is performed using a printing machine, a dispenser, or the like. The weir may be in an uncured state or a partially cured semi-cured state. When the curable resin composition for weir formation is a photocurable composition, partial curing of the weir is performed by light irradiation. For example, the photocurable resin composition is partially cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.).
(工程(α22))
工程(α21)の後、工程(α22)においては、堰で囲まれた領域に液状の粘着層形成用硬化性樹脂組成物を供給する。
粘着層形成用硬化性樹脂組成物の供給量は、堰、透明面材および保護フィルムによって形成される空間が粘着層形成用硬化性樹脂組成物によって充填され、かつ透明面材と保護フィルムとの間を所定の間隔とする(すなわち粘着層を所定の厚さとする)だけの分量にあらかじめ設定する。この際、粘着層形成用硬化性樹脂組成物の硬化収縮による体積減少をあらかじめ考慮することが好ましい。よって、該分量は、粘着層の所定厚さよりも粘着層形成用硬化性樹脂組成物の厚さが若干厚くなる量が好ましい。
供給方法としては、透明面材を平置きにし、ディスペンサ、ダイコータ等の供給手段によって、粘着層形成用硬化性樹脂組成物を点状、線状または面状に供給する方法が挙げられる。 (Process (α22))
After the step (α21), in the step (α22), a liquid adhesive layer forming curable resin composition is supplied to a region surrounded by the weir.
The supply amount of the curable resin composition for forming the adhesive layer is such that the space formed by the weir, the transparent surface material and the protective film is filled with the curable resin composition for forming the adhesive layer, and the transparent surface material and the protective film The amount is set in advance so that the interval is a predetermined interval (that is, the adhesive layer has a predetermined thickness). At this time, it is preferable to consider in advance volume reduction due to curing shrinkage of the curable resin composition for forming an adhesive layer. Therefore, the amount is preferably such that the thickness of the curable resin composition for forming an adhesive layer is slightly larger than the predetermined thickness of the adhesive layer.
Examples of the supply method include a method in which the transparent face material is placed flat and the adhesive layer-forming curable resin composition is supplied in the form of dots, lines or planes by a supply means such as a dispenser or a die coater.
工程(α21)の後、工程(α22)においては、堰で囲まれた領域に液状の粘着層形成用硬化性樹脂組成物を供給する。
粘着層形成用硬化性樹脂組成物の供給量は、堰、透明面材および保護フィルムによって形成される空間が粘着層形成用硬化性樹脂組成物によって充填され、かつ透明面材と保護フィルムとの間を所定の間隔とする(すなわち粘着層を所定の厚さとする)だけの分量にあらかじめ設定する。この際、粘着層形成用硬化性樹脂組成物の硬化収縮による体積減少をあらかじめ考慮することが好ましい。よって、該分量は、粘着層の所定厚さよりも粘着層形成用硬化性樹脂組成物の厚さが若干厚くなる量が好ましい。
供給方法としては、透明面材を平置きにし、ディスペンサ、ダイコータ等の供給手段によって、粘着層形成用硬化性樹脂組成物を点状、線状または面状に供給する方法が挙げられる。 (Process (α22))
After the step (α21), in the step (α22), a liquid adhesive layer forming curable resin composition is supplied to a region surrounded by the weir.
The supply amount of the curable resin composition for forming the adhesive layer is such that the space formed by the weir, the transparent surface material and the protective film is filled with the curable resin composition for forming the adhesive layer, and the transparent surface material and the protective film The amount is set in advance so that the interval is a predetermined interval (that is, the adhesive layer has a predetermined thickness). At this time, it is preferable to consider in advance volume reduction due to curing shrinkage of the curable resin composition for forming an adhesive layer. Therefore, the amount is preferably such that the thickness of the curable resin composition for forming an adhesive layer is slightly larger than the predetermined thickness of the adhesive layer.
Examples of the supply method include a method in which the transparent face material is placed flat and the adhesive layer-forming curable resin composition is supplied in the form of dots, lines or planes by a supply means such as a dispenser or a die coater.
(工程(β2))
工程(α22)の後、工程(β2)においては、粘着層形成用硬化性樹脂組成物が供給された透明面材を減圧装置に入れ、減圧装置内の固定支持盤の上に粘着層形成用硬化性樹脂組成物の面が上になるように透明面材を平置きする。
減圧装置内の上部には、上下方向に移動可能な移動支持機構が設けられ、移動支持機構に支持面材(ガラス板等)が取り付けられる。支持面材の下側の表面には保護フィルムが貼合される。
支持面材は、透明面材の上方かつ粘着層形成用硬化性樹脂組成物と接しない位置に置く。すなわち、透明面材の上の粘着層形成用硬化性樹脂組成物と支持面材の表面に貼合した保護フィルムとを接触させることなく対向させる。 (Process (β2))
After the step (α22), in the step (β2), the transparent surface material supplied with the curable resin composition for forming the adhesive layer is put into a decompression device, and the adhesive layer is formed on the fixed support disk in the decompression device. The transparent face material is laid flat so that the surface of the curable resin composition is on top.
A moving support mechanism that can move in the vertical direction is provided in the upper part of the decompression device, and a support surface material (such as a glass plate) is attached to the moving support mechanism. A protective film is bonded to the lower surface of the support surface material.
The supporting face material is placed above the transparent face material and at a position not in contact with the curable resin composition for forming the adhesive layer. That is, the curable resin composition for forming an adhesive layer on the transparent surface material and the protective film bonded to the surface of the support surface material are opposed to each other without being brought into contact with each other.
工程(α22)の後、工程(β2)においては、粘着層形成用硬化性樹脂組成物が供給された透明面材を減圧装置に入れ、減圧装置内の固定支持盤の上に粘着層形成用硬化性樹脂組成物の面が上になるように透明面材を平置きする。
減圧装置内の上部には、上下方向に移動可能な移動支持機構が設けられ、移動支持機構に支持面材(ガラス板等)が取り付けられる。支持面材の下側の表面には保護フィルムが貼合される。
支持面材は、透明面材の上方かつ粘着層形成用硬化性樹脂組成物と接しない位置に置く。すなわち、透明面材の上の粘着層形成用硬化性樹脂組成物と支持面材の表面に貼合した保護フィルムとを接触させることなく対向させる。 (Process (β2))
After the step (α22), in the step (β2), the transparent surface material supplied with the curable resin composition for forming the adhesive layer is put into a decompression device, and the adhesive layer is formed on the fixed support disk in the decompression device. The transparent face material is laid flat so that the surface of the curable resin composition is on top.
A moving support mechanism that can move in the vertical direction is provided in the upper part of the decompression device, and a support surface material (such as a glass plate) is attached to the moving support mechanism. A protective film is bonded to the lower surface of the support surface material.
The supporting face material is placed above the transparent face material and at a position not in contact with the curable resin composition for forming the adhesive layer. That is, the curable resin composition for forming an adhesive layer on the transparent surface material and the protective film bonded to the surface of the support surface material are opposed to each other without being brought into contact with each other.
透明面材および支持面材を所定の位置に配置した後、減圧装置の内部を減圧して所定の減圧雰囲気とする。減圧装置の内部が所定の減圧雰囲気となった後、移動支持機構で支持された支持面材を下方に移動し、透明面材の上の第一組成物の上に、保護フィルム付き支持面材を、保護フィルムの表面が粘着層形成用硬化性樹脂組成物に接するように重ね合わせる。以下、この重ね合わせたものを積層体という。
After placing the transparent face material and the support face material at predetermined positions, the inside of the pressure reducing device is depressurized to obtain a predetermined reduced pressure atmosphere. After the inside of the decompression device has a predetermined decompressed atmosphere, the support surface material supported by the moving support mechanism is moved downward, and the support surface material with a protective film is placed on the first composition on the transparent surface material. Are overlaid so that the surface of the protective film is in contact with the curable resin composition for forming an adhesive layer. Hereinafter, this superposition is referred to as a laminate.
重ね合わせによって、透明面材の表面、支持面材に貼合された保護フィルムの表面、および堰で囲まれた空間内に、粘着層形成用硬化性樹脂組成物が密封される。
重ね合わせの際、支持面材の自重、移動支持機構からの押圧等によって、粘着層形成用硬化性樹脂組成物が押し広げられ、前記空間内に粘着層形成用硬化性樹脂組成物が充満し、未硬化の粘着層が形成される。その後、工程(γ21)において高い圧力雰囲気に曝した際に、気泡の少ないまたは気泡のない未硬化の粘着層が形成される。 By the overlapping, the adhesive layer forming curable resin composition is sealed in the surface surrounded by the surface of the transparent surface material, the surface of the protective film bonded to the support surface material, and the weir.
During the stacking, the adhesive layer-forming curable resin composition is spread by the weight of the supporting surface material, the pressure from the moving support mechanism, etc., and the space is filled with the adhesive layer-forming curable resin composition. An uncured adhesive layer is formed. Thereafter, when exposed to a high pressure atmosphere in the step (γ21), an uncured adhesive layer with few or no bubbles is formed.
重ね合わせの際、支持面材の自重、移動支持機構からの押圧等によって、粘着層形成用硬化性樹脂組成物が押し広げられ、前記空間内に粘着層形成用硬化性樹脂組成物が充満し、未硬化の粘着層が形成される。その後、工程(γ21)において高い圧力雰囲気に曝した際に、気泡の少ないまたは気泡のない未硬化の粘着層が形成される。 By the overlapping, the adhesive layer forming curable resin composition is sealed in the surface surrounded by the surface of the transparent surface material, the surface of the protective film bonded to the support surface material, and the weir.
During the stacking, the adhesive layer-forming curable resin composition is spread by the weight of the supporting surface material, the pressure from the moving support mechanism, etc., and the space is filled with the adhesive layer-forming curable resin composition. An uncured adhesive layer is formed. Thereafter, when exposed to a high pressure atmosphere in the step (γ21), an uncured adhesive layer with few or no bubbles is formed.
重ね合わせの際の減圧雰囲気は、1kPa以下が好ましく、10~300Paがより好ましく、15~100Paがさらに好ましい。減圧雰囲気が極度に低圧であると、粘着層形成用硬化性樹脂組成物に含まれる各成分(硬化性化合物、光重合開始剤、重合禁止剤、連鎖移動剤、光安定剤等)に悪影響を与えるおそれがある。たとえば、減圧雰囲気が極度に低圧であると、各成分が気化するおそれがあり、また、減圧雰囲気を提供するために時間がかかることがある。
The reduced pressure atmosphere at the time of superposition is preferably 1 kPa or less, more preferably 10 to 300 Pa, and further preferably 15 to 100 Pa. If the reduced-pressure atmosphere is extremely low, each component (curable compound, photopolymerization initiator, polymerization inhibitor, chain transfer agent, light stabilizer, etc.) contained in the curable resin composition for forming an adhesive layer will be adversely affected. There is a risk of giving. For example, if the reduced-pressure atmosphere is extremely low pressure, each component may be vaporized, and it may take time to provide the reduced-pressure atmosphere.
透明面材と支持面材とを重ね合わせた時点から減圧雰囲気を解除するまでの時間は、特に限定されず、粘着層形成用硬化性樹脂組成物の密封後、直ちに減圧雰囲気を解除してもよく、粘着層形成用硬化性樹脂組成物の密封後、減圧状態を所定時間維持してもよい。
The time from when the transparent surface material and the support surface material are overlapped to when the reduced pressure atmosphere is released is not particularly limited, and even after the reduced pressure atmosphere is released immediately after sealing the curable resin composition for forming the adhesive layer. Alternatively, after sealing the curable resin composition for forming an adhesive layer, the reduced pressure state may be maintained for a predetermined time.
(工程(γ21))
工程(β2)における減圧雰囲気を解除した後、工程(γ21)として、積層体を工程(β2)より高い圧力雰囲気下に置く。工程(β2)より高い圧力雰囲気としては、50kPa以上の圧力雰囲気が好ましい。
積層体を工程(β2)より高い圧力雰囲気下に置くと、上昇した圧力によって透明面材と支持面材とが密着する方向に押圧される。そのため、積層体内の密閉空間に気泡が存在すると、気泡に未硬化の粘着層が流動していき、密閉空間全体が未硬化の粘着層によって均一に充填される。 (Process (γ21))
After releasing the reduced pressure atmosphere in the step (β2), as a step (γ21), the laminate is placed in a higher pressure atmosphere than in the step (β2). As a pressure atmosphere higher than the step (β2), a pressure atmosphere of 50 kPa or more is preferable.
When the laminate is placed in a higher pressure atmosphere than in the step (β2), the pressure is increased in the direction in which the transparent surface material and the support surface material are in close contact with each other. Therefore, if bubbles exist in the sealed space in the laminate, the uncured adhesive layer flows into the bubbles, and the entire sealed space is uniformly filled with the uncured adhesive layer.
工程(β2)における減圧雰囲気を解除した後、工程(γ21)として、積層体を工程(β2)より高い圧力雰囲気下に置く。工程(β2)より高い圧力雰囲気としては、50kPa以上の圧力雰囲気が好ましい。
積層体を工程(β2)より高い圧力雰囲気下に置くと、上昇した圧力によって透明面材と支持面材とが密着する方向に押圧される。そのため、積層体内の密閉空間に気泡が存在すると、気泡に未硬化の粘着層が流動していき、密閉空間全体が未硬化の粘着層によって均一に充填される。 (Process (γ21))
After releasing the reduced pressure atmosphere in the step (β2), as a step (γ21), the laminate is placed in a higher pressure atmosphere than in the step (β2). As a pressure atmosphere higher than the step (β2), a pressure atmosphere of 50 kPa or more is preferable.
When the laminate is placed in a higher pressure atmosphere than in the step (β2), the pressure is increased in the direction in which the transparent surface material and the support surface material are in close contact with each other. Therefore, if bubbles exist in the sealed space in the laminate, the uncured adhesive layer flows into the bubbles, and the entire sealed space is uniformly filled with the uncured adhesive layer.
積層体を工程(β2)より高い圧力雰囲気下に置いた時点から未硬化の粘着層の硬化を開始するまでの時間(以下、高圧保持時間と記す。)は、特に限定されない。積層体を減圧装置から取り出して硬化装置に移動し、硬化を開始するまでのプロセスを大気圧雰囲気下で行う場合には、そのプロセスに要する時間が高圧保持時間となる。
よって、大気圧雰囲気下に置いた時点ですでに積層体の密閉空間内に気泡が存在しない場合、またはそのプロセスの間に気泡が消滅した場合は、直ちに未硬化の粘着層を硬化させることができる。気泡が消滅するまでに時間を要する場合は、積層体を気泡が消滅するまで工程(β2)より高い圧力雰囲気下で保持する。また、高圧保持時間が長くなっても通常支障は生じないことから、プロセス上の他の必要性から高圧保持時間を長くしてもよい。高圧保持時間は、1日以上の長時間であってもよいが、生産効率の点から、6時間以内が好ましく、1時間以内がより好ましく、さらに生産効率が高まる点から、10分以内が特に好ましい。 The time from when the laminate is placed in a higher pressure atmosphere than in the step (β2) to the start of curing of the uncured adhesive layer (hereinafter referred to as “high pressure holding time”) is not particularly limited. When the process from taking out the laminated body from the decompression device to the curing device and starting the curing is performed under an atmospheric pressure atmosphere, the time required for the process becomes the high pressure holding time.
Therefore, if there are no air bubbles in the sealed space of the laminate when placed in an atmospheric pressure atmosphere, or if the air bubbles disappear during the process, the uncured adhesive layer can be cured immediately. it can. When it takes time until the bubbles disappear, the laminate is held under a higher pressure atmosphere than the step (β2) until the bubbles disappear. In addition, since there is usually no problem even if the high pressure holding time is increased, the high pressure holding time may be increased due to other necessity in the process. The high-pressure holding time may be a long time of one day or longer, but is preferably within 6 hours from the viewpoint of production efficiency, more preferably within 1 hour, and particularly within 10 minutes from the viewpoint of further increasing production efficiency. preferable.
よって、大気圧雰囲気下に置いた時点ですでに積層体の密閉空間内に気泡が存在しない場合、またはそのプロセスの間に気泡が消滅した場合は、直ちに未硬化の粘着層を硬化させることができる。気泡が消滅するまでに時間を要する場合は、積層体を気泡が消滅するまで工程(β2)より高い圧力雰囲気下で保持する。また、高圧保持時間が長くなっても通常支障は生じないことから、プロセス上の他の必要性から高圧保持時間を長くしてもよい。高圧保持時間は、1日以上の長時間であってもよいが、生産効率の点から、6時間以内が好ましく、1時間以内がより好ましく、さらに生産効率が高まる点から、10分以内が特に好ましい。 The time from when the laminate is placed in a higher pressure atmosphere than in the step (β2) to the start of curing of the uncured adhesive layer (hereinafter referred to as “high pressure holding time”) is not particularly limited. When the process from taking out the laminated body from the decompression device to the curing device and starting the curing is performed under an atmospheric pressure atmosphere, the time required for the process becomes the high pressure holding time.
Therefore, if there are no air bubbles in the sealed space of the laminate when placed in an atmospheric pressure atmosphere, or if the air bubbles disappear during the process, the uncured adhesive layer can be cured immediately. it can. When it takes time until the bubbles disappear, the laminate is held under a higher pressure atmosphere than the step (β2) until the bubbles disappear. In addition, since there is usually no problem even if the high pressure holding time is increased, the high pressure holding time may be increased due to other necessity in the process. The high-pressure holding time may be a long time of one day or longer, but is preferably within 6 hours from the viewpoint of production efficiency, more preferably within 1 hour, and particularly within 10 minutes from the viewpoint of further increasing production efficiency. preferable.
ついで、未硬化の粘着層および未硬化または半硬化の堰を硬化させることによって、粘着層および堰が形成される。この際、未硬化または半硬化の堰は、未硬化の粘着層の硬化と同時に硬化させてもよく、未硬化の粘着層の硬化の前にあらかじめ硬化させてもよい。
Then, the adhesive layer and the weir are formed by curing the uncured adhesive layer and the uncured or semi-cured weir. At this time, the uncured or semi-cured weir may be cured simultaneously with the curing of the uncured adhesive layer, or may be cured in advance before the uncured adhesive layer is cured.
未硬化の粘着層および未硬化または半硬化の堰は、光硬化性組成物からなる場合、光を照射して硬化させる。たとえば、光源(紫外線ランプ、高圧水銀灯、UV-LED等)から紫外線または短波長の可視光を照射して、光硬化性樹脂組成物を硬化させる。透明面材の周縁部に遮光印刷部が形成されている場合、または透明面材に反射防止層が設けられ、反射防止層、または反射防止層を形成した透明樹脂フィルムやその反射防止フィルムと透明面材との間に設けられた粘着層等が紫外線を透過しない場合は、支持面材の側から光を照射する。
When the uncured adhesive layer and the uncured or semi-cured weir are made of a photocurable composition, they are cured by irradiation with light. For example, the photocurable resin composition is cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.). When a light-shielding printing part is formed on the peripheral edge of the transparent surface material, or a transparent resin film on which an antireflection layer is provided on the transparent surface material and an antireflection layer is formed, or the antireflection film and its transparent When an adhesive layer or the like provided between the face material does not transmit ultraviolet rays, light is irradiated from the support face material side.
(工程(γ22))
工程(γ22)において、支持面材を保護フィルムから剥離することによって、充分な粘着力を有する粘着層が、あらかじめ透明面材に形成され、かつ透明面材と粘着層との界面における気泡の発生が充分に抑えられた、粘着層付き透明面材が得られる。 (Process (γ22))
In the step (γ22), the support surface material is peeled off from the protective film, whereby an adhesive layer having sufficient adhesive strength is formed in advance on the transparent surface material, and bubbles are generated at the interface between the transparent surface material and the adhesive layer. A transparent surface material with an adhesive layer in which is sufficiently suppressed can be obtained.
工程(γ22)において、支持面材を保護フィルムから剥離することによって、充分な粘着力を有する粘着層が、あらかじめ透明面材に形成され、かつ透明面材と粘着層との界面における気泡の発生が充分に抑えられた、粘着層付き透明面材が得られる。 (Process (γ22))
In the step (γ22), the support surface material is peeled off from the protective film, whereby an adhesive layer having sufficient adhesive strength is formed in advance on the transparent surface material, and bubbles are generated at the interface between the transparent surface material and the adhesive layer. A transparent surface material with an adhesive layer in which is sufficiently suppressed can be obtained.
[第2の実施形態の粘着層付き透明面材の製造方法]
以下、第2の実施形態の粘着層付き透明面材2の製造方法の一例を、図面を用いて具体的に説明する。この製造は、下記するα21、α22、β2、γ21、γ22の各工程をこの順に従って行われる。 [Method for Producing Transparent Surface Material with Adhesive Layer of Second Embodiment]
Hereinafter, an example of the manufacturing method of thetransparent surface material 2 with the adhesion layer of 2nd Embodiment is demonstrated concretely using drawing. In this production, the following steps α21, α22, β2, γ21, and γ22 are performed in this order.
以下、第2の実施形態の粘着層付き透明面材2の製造方法の一例を、図面を用いて具体的に説明する。この製造は、下記するα21、α22、β2、γ21、γ22の各工程をこの順に従って行われる。 [Method for Producing Transparent Surface Material with Adhesive Layer of Second Embodiment]
Hereinafter, an example of the manufacturing method of the
(工程(α21))
図6および図7に示すように、透明面材10の周縁部の遮光印刷部12に沿ってディスペンサ(図示略)等によって第二組成物を塗布して未硬化の堰22を形成する。 (Process (α21))
As shown in FIGS. 6 and 7, the second composition is applied by a dispenser (not shown) or the like along the lightshielding printing portion 12 at the peripheral edge of the transparent face material 10 to form an uncured weir 22.
図6および図7に示すように、透明面材10の周縁部の遮光印刷部12に沿ってディスペンサ(図示略)等によって第二組成物を塗布して未硬化の堰22を形成する。 (Process (α21))
As shown in FIGS. 6 and 7, the second composition is applied by a dispenser (not shown) or the like along the light
(工程(α22))
ついで、図8および図9に示すように、透明面材10の未硬化の堰22に囲まれた矩形状の領域24に第一組成物26を供給する。第一組成物26の供給量は、未硬化の堰22と透明面材10と保護フィルム16(図10参照)とによって密閉される空間が第一組成物26によって充填されるだけの量にあらかじめ設定されている。 (Process (α22))
Next, as shown in FIGS. 8 and 9, thefirst composition 26 is supplied to a rectangular region 24 surrounded by the uncured weir 22 of the transparent surface material 10. The supply amount of the first composition 26 is set in advance so that the space sealed by the uncured weir 22, the transparent face material 10, and the protective film 16 (see FIG. 10) is filled with the first composition 26. Is set.
ついで、図8および図9に示すように、透明面材10の未硬化の堰22に囲まれた矩形状の領域24に第一組成物26を供給する。第一組成物26の供給量は、未硬化の堰22と透明面材10と保護フィルム16(図10参照)とによって密閉される空間が第一組成物26によって充填されるだけの量にあらかじめ設定されている。 (Process (α22))
Next, as shown in FIGS. 8 and 9, the
第一組成物26の供給は、図8および図9に示すように、透明面材10を下定盤28に平置きにし、水平方向に移動するディスペンサ30によって第一組成物26を線状、帯状または点状に供給することによって実施される。
ディスペンサ30は、一対の送りねじ32と、送りねじ32に直交する送りねじ34とからなる公知の水平移動機構によって、領域24の全範囲において水平移動可能となっている。ディスペンサ30に代えて、ダイコータを用いてもよい。 As shown in FIG. 8 and FIG. 9, thefirst composition 26 is supplied by placing the transparent surface material 10 flat on the lower platen 28 and moving the first composition 26 into a linear or belt shape by a dispenser 30 that moves in the horizontal direction. Or it implements by supplying in a dot form.
Thedispenser 30 is horizontally movable in the entire range of the region 24 by a known horizontal movement mechanism including a pair of feed screws 32 and a feed screw 34 orthogonal to the feed screw 32. Instead of the dispenser 30, a die coater may be used.
ディスペンサ30は、一対の送りねじ32と、送りねじ32に直交する送りねじ34とからなる公知の水平移動機構によって、領域24の全範囲において水平移動可能となっている。ディスペンサ30に代えて、ダイコータを用いてもよい。 As shown in FIG. 8 and FIG. 9, the
The
(工程(β2))
ついで、図10に示すように、透明面材10と、保護フィルム16付き支持面材36とを減圧装置38内に搬入する。減圧装置38内の上部には、複数の吸着パッド40を有する上定盤42が配置され、下部には、下定盤44が設けられている。上定盤42は、エアシリンダ46によって上下方向に移動可能とされている。
支持面材36は、保護フィルム16が貼合された面を下にして吸着パッド40に取り付けられる。透明面材10は、第一組成物26が供給された面を上にして下定盤44の上に固定される。 (Process (β2))
Next, as shown in FIG. 10, thetransparent surface material 10 and the support surface material 36 with the protective film 16 are carried into the decompression device 38. An upper surface plate 42 having a plurality of suction pads 40 is disposed in the upper portion of the decompression device 38, and a lower surface plate 44 is disposed in the lower portion. The upper surface plate 42 can be moved in the vertical direction by an air cylinder 46.
Thesupport surface material 36 is attached to the suction pad 40 with the surface to which the protective film 16 is bonded facing down. The transparent surface material 10 is fixed on the lower surface plate 44 with the surface to which the first composition 26 is supplied facing up.
ついで、図10に示すように、透明面材10と、保護フィルム16付き支持面材36とを減圧装置38内に搬入する。減圧装置38内の上部には、複数の吸着パッド40を有する上定盤42が配置され、下部には、下定盤44が設けられている。上定盤42は、エアシリンダ46によって上下方向に移動可能とされている。
支持面材36は、保護フィルム16が貼合された面を下にして吸着パッド40に取り付けられる。透明面材10は、第一組成物26が供給された面を上にして下定盤44の上に固定される。 (Process (β2))
Next, as shown in FIG. 10, the
The
ついで、減圧装置38内の空気を真空ポンプ48によって吸引する。減圧装置38内の雰囲気圧力が、たとえば15~100Paの減圧雰囲気に達した後、支持面材36を上定盤42の吸着パッド40によって吸着保持した状態で、下に待機している透明面材10に向けて、エアシリンダ46を動作させて下降させる。そして、透明面材10と、保護フィルム16付き支持面材36とを、未硬化の堰22を介して重ね合わせる。このように、透明面材10、保護フィルム16および未硬化の堰22で第一組成物26からなる未硬化の粘着層が密封された積層体を構成し、減圧雰囲気下で所定時間積層体を保持する。
Then, the air in the decompression device 38 is sucked by the vacuum pump 48. After the atmospheric pressure in the decompression device 38 reaches, for example, a reduced pressure atmosphere of 15 to 100 Pa, the transparent surface material waiting underneath while the support surface material 36 is adsorbed and held by the adsorption pad 40 of the upper surface plate 42. 10, the air cylinder 46 is operated and lowered. And the transparent surface material 10 and the support surface material 36 with the protective film 16 are piled up through the uncured weir 22. Thus, the transparent body 10, the protective film 16, and the uncured weir 22 constitute a laminated body in which the uncured adhesive layer made of the first composition 26 is sealed, and the laminated body is formed for a predetermined time in a reduced-pressure atmosphere. Hold.
(工程(γ21))
ついで、減圧装置38の内部をたとえば大気圧雰囲気にした後、積層体を減圧装置38から取り出す。積層体を大気圧雰囲気下に置くと、積層体の透明面材10側の表面と支持面材36側の表面とが大気圧によって押圧され、密閉空間内の未硬化の粘着層が透明面材10と支持面材36とで加圧される。この圧力によって、密閉空間内の未硬化の粘着層が流動して、密閉空間全体が未硬化の粘着層によって均一に充填される。 (Process (γ21))
Next, after making the inside of thedecompression device 38 into an atmospheric pressure atmosphere, for example, the laminate is taken out from the decompression device 38. When the laminate is placed in an atmospheric pressure atmosphere, the surface of the laminate on the transparent face material 10 side and the surface on the support face material 36 side are pressed by atmospheric pressure, and the uncured adhesive layer in the sealed space becomes a transparent face material. 10 and the support surface material 36 are pressurized. By this pressure, the uncured adhesive layer in the sealed space flows, and the entire sealed space is uniformly filled with the uncured adhesive layer.
ついで、減圧装置38の内部をたとえば大気圧雰囲気にした後、積層体を減圧装置38から取り出す。積層体を大気圧雰囲気下に置くと、積層体の透明面材10側の表面と支持面材36側の表面とが大気圧によって押圧され、密閉空間内の未硬化の粘着層が透明面材10と支持面材36とで加圧される。この圧力によって、密閉空間内の未硬化の粘着層が流動して、密閉空間全体が未硬化の粘着層によって均一に充填される。 (Process (γ21))
Next, after making the inside of the
ついで、支持面材36の側から未硬化の堰22および未硬化の粘着層に光(紫外線や短波長の可視光)を照射し、積層体内部の未硬化の堰22および未硬化の粘着層を硬化させ、粘着層14および堰15を形成する。
Next, the uncured weir 22 and the uncured adhesive layer are irradiated with light (ultraviolet rays and visible light having a short wavelength) from the support surface material 36 side, and the uncured weir 22 and the uncured adhesive layer inside the laminate are then irradiated. Is cured to form the adhesive layer 14 and the weir 15.
(工程(γ22))
ついで、支持面材36を保護フィルム16から剥離することによって、図2に示す粘着層付き透明面材2が得られる。 (Process (γ22))
Subsequently, thesupport surface material 36 is peeled from the protective film 16 to obtain the transparent surface material 2 with the adhesive layer shown in FIG.
ついで、支持面材36を保護フィルム16から剥離することによって、図2に示す粘着層付き透明面材2が得られる。 (Process (γ22))
Subsequently, the
(他の実施形態)
本発明の粘着層付き透明面材の製造方法は、本発明の粘着層付き透明面材を製造する方法であって、工程(α)および工程(γ)を有する方法であればよく、図示例の粘着層付き透明面材の製造方法には限定されない。
たとえば、粘着層付き透明面材の保護フィルムの周縁部を、減圧条件下で、全周にわたって透明面材に気密に接合してもよい。具体的には、図1に示す粘着層付き透明面材1の保護フィルム16の周縁部を、減圧条件下で、全周にわたり透明面材10のいずれかの位置(側面、下面、上面等)に気密に接合してもよい。これによって、粘着層14は、保護フィルム16に気密に包み込まれることとなるため、粘着層14への外気混入を確実に防止できる。
また、粘着層付き透明面材を、減圧条件下で、ガスバリア性を有するフィルムからなる封入体に封入してもよい。これによって、粘着層への外気混入の防止を図ることもできる。 (Other embodiments)
The method for producing a transparent surface material with an adhesive layer of the present invention is a method for producing the transparent surface material with an adhesive layer of the present invention, as long as it is a method having a step (α) and a step (γ). It is not limited to the manufacturing method of the transparent surface material with an adhesion layer.
For example, the peripheral edge portion of the protective film of the transparent surface material with the adhesive layer may be airtightly bonded to the transparent surface material over the entire circumference under reduced pressure conditions. Specifically, the peripheral portion of theprotective film 16 of the transparent surface material 1 with the adhesive layer shown in FIG. 1 is placed at any position (side surface, lower surface, upper surface, etc.) of the transparent surface material 10 over the entire circumference under reduced pressure conditions. May be joined airtightly. As a result, the adhesive layer 14 is hermetically wrapped in the protective film 16, so it is possible to reliably prevent outside air from being mixed into the adhesive layer 14.
Moreover, you may enclose the transparent surface material with an adhesion layer in the enclosure which consists of a film which has gas barrier property on pressure reduction conditions. Thereby, it is possible to prevent the outside air from being mixed into the adhesive layer.
本発明の粘着層付き透明面材の製造方法は、本発明の粘着層付き透明面材を製造する方法であって、工程(α)および工程(γ)を有する方法であればよく、図示例の粘着層付き透明面材の製造方法には限定されない。
たとえば、粘着層付き透明面材の保護フィルムの周縁部を、減圧条件下で、全周にわたって透明面材に気密に接合してもよい。具体的には、図1に示す粘着層付き透明面材1の保護フィルム16の周縁部を、減圧条件下で、全周にわたり透明面材10のいずれかの位置(側面、下面、上面等)に気密に接合してもよい。これによって、粘着層14は、保護フィルム16に気密に包み込まれることとなるため、粘着層14への外気混入を確実に防止できる。
また、粘着層付き透明面材を、減圧条件下で、ガスバリア性を有するフィルムからなる封入体に封入してもよい。これによって、粘着層への外気混入の防止を図ることもできる。 (Other embodiments)
The method for producing a transparent surface material with an adhesive layer of the present invention is a method for producing the transparent surface material with an adhesive layer of the present invention, as long as it is a method having a step (α) and a step (γ). It is not limited to the manufacturing method of the transparent surface material with an adhesion layer.
For example, the peripheral edge portion of the protective film of the transparent surface material with the adhesive layer may be airtightly bonded to the transparent surface material over the entire circumference under reduced pressure conditions. Specifically, the peripheral portion of the
Moreover, you may enclose the transparent surface material with an adhesion layer in the enclosure which consists of a film which has gas barrier property on pressure reduction conditions. Thereby, it is possible to prevent the outside air from being mixed into the adhesive layer.
(作用機序)
以上説明した本発明の粘着層付き透明面材の製造方法にあっては、本発明の粘着層付き透明面材を製造する方法であって、工程(α)および工程(γ)を有するため、被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材を製造できる。 (Mechanism of action)
In the method for producing a transparent surface material with an adhesive layer of the present invention described above, the method for producing the transparent surface material with an adhesive layer of the present invention, comprising the step (α) and the step (γ), When bonded to the object to be bonded, it is possible to produce a transparent surface material with an adhesive layer in which bubbles remaining at the interface between the object to be bonded and the adhesive layer can quickly disappear.
以上説明した本発明の粘着層付き透明面材の製造方法にあっては、本発明の粘着層付き透明面材を製造する方法であって、工程(α)および工程(γ)を有するため、被貼合物と貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し得る粘着層付き透明面材を製造できる。 (Mechanism of action)
In the method for producing a transparent surface material with an adhesive layer of the present invention described above, the method for producing the transparent surface material with an adhesive layer of the present invention, comprising the step (α) and the step (γ), When bonded to the object to be bonded, it is possible to produce a transparent surface material with an adhesive layer in which bubbles remaining at the interface between the object to be bonded and the adhesive layer can quickly disappear.
<表示装置>
図11は、本発明の表示装置の一例を示す断面図である。
表示装置3は、表示パネル50と、粘着層14が表示パネル50に接するように、表示パネル50に貼合された、粘着層付き透明面材2とを有する。
表示装置3は、透明面材10と、表示パネル50と、透明面材10および表示パネル50に挟まれた粘着層14と、粘着層14の周囲を囲む堰15と、表示パネル50に接続された表示パネル50を動作させる駆動ICを搭載したフレキシブルプリント配線板60(FPC)とを有する。 <Display device>
FIG. 11 is a cross-sectional view illustrating an example of the display device of the present invention.
The display device 3 includes thedisplay panel 50 and the transparent surface material 2 with the adhesive layer bonded to the display panel 50 so that the adhesive layer 14 contacts the display panel 50.
The display device 3 is connected to thetransparent surface material 10, the display panel 50, the adhesive layer 14 sandwiched between the transparent surface material 10 and the display panel 50, the weir 15 surrounding the adhesive layer 14, and the display panel 50. And a flexible printed wiring board 60 (FPC) on which a driving IC for operating the display panel 50 is mounted.
図11は、本発明の表示装置の一例を示す断面図である。
表示装置3は、表示パネル50と、粘着層14が表示パネル50に接するように、表示パネル50に貼合された、粘着層付き透明面材2とを有する。
表示装置3は、透明面材10と、表示パネル50と、透明面材10および表示パネル50に挟まれた粘着層14と、粘着層14の周囲を囲む堰15と、表示パネル50に接続された表示パネル50を動作させる駆動ICを搭載したフレキシブルプリント配線板60(FPC)とを有する。 <Display device>
FIG. 11 is a cross-sectional view illustrating an example of the display device of the present invention.
The display device 3 includes the
The display device 3 is connected to the
(表示パネル)
図11に示すように、表示パネル50は、カラーフィルタを設けた透明基板52とTFTを設けた透明基板54とが液晶層56を挟んで貼合され、これが一対の偏光板58によって挟持された構成の液晶パネルの一例である。 (Display panel)
As shown in FIG. 11, in thedisplay panel 50, a transparent substrate 52 provided with a color filter and a transparent substrate 54 provided with a TFT are bonded with a liquid crystal layer 56 interposed therebetween, and this is sandwiched between a pair of polarizing plates 58. It is an example of the liquid crystal panel of a structure.
図11に示すように、表示パネル50は、カラーフィルタを設けた透明基板52とTFTを設けた透明基板54とが液晶層56を挟んで貼合され、これが一対の偏光板58によって挟持された構成の液晶パネルの一例である。 (Display panel)
As shown in FIG. 11, in the
表示パネル50の粘着層14との接合面には、粘着層14との密着性を向上させるために、表面処理を施してもよい。表面処理は、周縁部だけであってもよく、面材の表面全体であってもよい。表面処理の方法としては、低温加工可能な接着用プライマー等で処理する方法等が挙げられる。
表示パネル50の厚さは、TFTによって動作させる液晶パネルの場合は0.4~4mm程度であり、ELパネルの場合は0.2~3mm程度であることが多い。 In order to improve adhesiveness with theadhesion layer 14, you may surface-treat to the joint surface with the adhesion layer 14 of the display panel 50. FIG. The surface treatment may be performed only on the peripheral edge or on the entire surface of the face material. Examples of the surface treatment method include a treatment method using an adhesion primer or the like which can be processed at a low temperature.
The thickness of thedisplay panel 50 is about 0.4 to 4 mm in the case of a liquid crystal panel operated by TFT, and is often about 0.2 to 3 mm in the case of an EL panel.
表示パネル50の厚さは、TFTによって動作させる液晶パネルの場合は0.4~4mm程度であり、ELパネルの場合は0.2~3mm程度であることが多い。 In order to improve adhesiveness with the
The thickness of the
(形状)
表示パネル50の形状は、一般的には矩形である。透明面材10と表示パネル50の寸法は、ほぼ等しくてもよいし、表示装置を収納する他の筺体との関係から、透明面材10を表示パネル50より一回り大きくしてもよい。また逆に、他の筺体の構造によっては、透明面材10を表示パネル50より若干小さくしてもよい。 (shape)
The shape of thedisplay panel 50 is generally a rectangle. The dimensions of the transparent surface material 10 and the display panel 50 may be substantially equal, or the transparent surface material 10 may be made slightly larger than the display panel 50 in view of the relationship with the other housing that houses the display device. Conversely, the transparent surface material 10 may be slightly smaller than the display panel 50 depending on the structure of another casing.
表示パネル50の形状は、一般的には矩形である。透明面材10と表示パネル50の寸法は、ほぼ等しくてもよいし、表示装置を収納する他の筺体との関係から、透明面材10を表示パネル50より一回り大きくしてもよい。また逆に、他の筺体の構造によっては、透明面材10を表示パネル50より若干小さくしてもよい。 (shape)
The shape of the
(他の実施形態)
本発明の表示装置は、表示パネルに本発明の粘着層付き透明面材が貼合されたものであればよく、図示例のものに限定はされない。
たとえば、表示パネルは、図11に示した液晶パネルに限定されない。
表示パネルは、少なくとも一方が透明電極である一対の電極間や、同一面内に形成された複数の電極対を有する基板と透明基板との間などに、外部の電気信号によって光学特性が変化する表示材を挟持したものである。表示材の種類によって、液晶パネル、ELパネル、プラズマパネル、電子インク型パネル等がある。
また、表示パネルは、少なくとも一方が透明基板である一対の面材を貼り合わせた構造を有しており、透明基板側が粘着層と接するように配置する。この際、一部の表示パネルにおいては、粘着層と接する側の透明基板の最外層側に偏光板、位相差板等の光学フィルムが設置されていることがある。この場合、粘着層は、表示パネル上の光学フィルムと透明面材とを接合する様態となる。 (Other embodiments)
The display apparatus of this invention should just be what the transparent surface material with the adhesion layer of this invention was bonded by the display panel, and is not limited to the thing of the example of illustration.
For example, the display panel is not limited to the liquid crystal panel shown in FIG.
The display panel changes in optical characteristics by an external electric signal between a pair of electrodes, at least one of which is a transparent electrode, or between a substrate having a plurality of electrode pairs formed in the same plane and a transparent substrate. The display material is sandwiched. There are liquid crystal panels, EL panels, plasma panels, electronic ink panels, and the like depending on the type of display material.
Further, the display panel has a structure in which a pair of face materials, at least one of which is a transparent substrate, is bonded, and is arranged so that the transparent substrate side is in contact with the adhesive layer. At this time, in some display panels, an optical film such as a polarizing plate or a retardation plate may be provided on the outermost layer side of the transparent substrate on the side in contact with the adhesive layer. In this case, the adhesive layer is in a state of joining the optical film on the display panel and the transparent surface material.
本発明の表示装置は、表示パネルに本発明の粘着層付き透明面材が貼合されたものであればよく、図示例のものに限定はされない。
たとえば、表示パネルは、図11に示した液晶パネルに限定されない。
表示パネルは、少なくとも一方が透明電極である一対の電極間や、同一面内に形成された複数の電極対を有する基板と透明基板との間などに、外部の電気信号によって光学特性が変化する表示材を挟持したものである。表示材の種類によって、液晶パネル、ELパネル、プラズマパネル、電子インク型パネル等がある。
また、表示パネルは、少なくとも一方が透明基板である一対の面材を貼り合わせた構造を有しており、透明基板側が粘着層と接するように配置する。この際、一部の表示パネルにおいては、粘着層と接する側の透明基板の最外層側に偏光板、位相差板等の光学フィルムが設置されていることがある。この場合、粘着層は、表示パネル上の光学フィルムと透明面材とを接合する様態となる。 (Other embodiments)
The display apparatus of this invention should just be what the transparent surface material with the adhesion layer of this invention was bonded by the display panel, and is not limited to the thing of the example of illustration.
For example, the display panel is not limited to the liquid crystal panel shown in FIG.
The display panel changes in optical characteristics by an external electric signal between a pair of electrodes, at least one of which is a transparent electrode, or between a substrate having a plurality of electrode pairs formed in the same plane and a transparent substrate. The display material is sandwiched. There are liquid crystal panels, EL panels, plasma panels, electronic ink panels, and the like depending on the type of display material.
Further, the display panel has a structure in which a pair of face materials, at least one of which is a transparent substrate, is bonded, and is arranged so that the transparent substrate side is in contact with the adhesive layer. At this time, in some display panels, an optical film such as a polarizing plate or a retardation plate may be provided on the outermost layer side of the transparent substrate on the side in contact with the adhesive layer. In this case, the adhesive layer is in a state of joining the optical film on the display panel and the transparent surface material.
(作用機序)
以上説明した本発明の表示装置にあっては、表示パネルに本発明の粘着層付き透明面材が貼合されたものであるため、表示パネルと粘着層との界面への気泡の残存が抑えられたものとなる。 (Mechanism of action)
In the display device of the present invention described above, since the transparent surface material with the adhesive layer of the present invention is bonded to the display panel, the remaining of bubbles at the interface between the display panel and the adhesive layer is suppressed. It will be
以上説明した本発明の表示装置にあっては、表示パネルに本発明の粘着層付き透明面材が貼合されたものであるため、表示パネルと粘着層との界面への気泡の残存が抑えられたものとなる。 (Mechanism of action)
In the display device of the present invention described above, since the transparent surface material with the adhesive layer of the present invention is bonded to the display panel, the remaining of bubbles at the interface between the display panel and the adhesive layer is suppressed. It will be
<表示装置の製造方法>
本発明の表示装置を製造するには、本発明の粘着層付き透明面材から保護フィルム(保護材)を剥離した後、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねて貼合する。
表示装置の製造方法は、以下に示す工程S1、S2を含む方法であってよい。 <Manufacturing method of display device>
In order to manufacture the display device of the present invention, the protective film (protective material) is peeled from the transparent surface material with the adhesive layer of the present invention, and then the display panel and the transparent surface material with the adhesive layer are bonded to the display panel. Laminate to touch.
The manufacturing method of the display device may be a method including steps S1 and S2 described below.
本発明の表示装置を製造するには、本発明の粘着層付き透明面材から保護フィルム(保護材)を剥離した後、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねて貼合する。
表示装置の製造方法は、以下に示す工程S1、S2を含む方法であってよい。 <Manufacturing method of display device>
In order to manufacture the display device of the present invention, the protective film (protective material) is peeled from the transparent surface material with the adhesive layer of the present invention, and then the display panel and the transparent surface material with the adhesive layer are bonded to the display panel. Laminate to touch.
The manufacturing method of the display device may be a method including steps S1 and S2 described below.
(工程S1:保護フィルム剥離工程)
該工程では、粘着層が保護フィルムによって覆われた粘着層付き透明面材から保護フィルムを剥離する。保護フィルムの剥離は、大気中で実施してもよいし、減圧雰囲気下で実施してもよい。保護フィルムを剥離した後、工程S2で用いる減圧容器の内部に粘着層付き透明面材を移送するまでの間、粘着層付き透明面材を大気中に晒すことなく、減圧雰囲気下に保管できるのであれば、保護フィルムの剥離を減圧雰囲気下で実施することが好ましい。
ただし、生産設備等の都合上、保護フィルムの剥離を減圧雰囲気下で実施することは実際には困難であることが多い。その場合、保護フィルムの剥離を大気中で実施しても特に問題はない。保護フィルム剥離工程に減圧容器を準備する必要がない点では、保護フィルムの剥離を大気中で実施することが好ましい。保護フィルムの剥離後は、速やかに次の工程S2を行うことが好ましい。 (Step S1: Protective film peeling step)
In this step, the protective film is peeled from the transparent surface material with the adhesive layer, which is covered with the protective film. The protective film may be peeled in the air or in a reduced pressure atmosphere. After the protective film is peeled off, the transparent surface material with the adhesive layer can be stored in a reduced pressure atmosphere without being exposed to the atmosphere until the transparent surface material with the adhesive layer is transferred to the inside of the vacuum container used in the step S2. If it exists, it is preferable to carry out peeling of the protective film under a reduced pressure atmosphere.
However, it is often difficult to actually remove the protective film in a reduced pressure atmosphere due to production facilities and the like. In that case, there is no particular problem even if the protective film is peeled off in the air. It is preferable to carry out the peeling of the protective film in the air in that it is not necessary to prepare a vacuum container for the protective film peeling step. After the protective film is peeled off, it is preferable to immediately perform the next step S2.
該工程では、粘着層が保護フィルムによって覆われた粘着層付き透明面材から保護フィルムを剥離する。保護フィルムの剥離は、大気中で実施してもよいし、減圧雰囲気下で実施してもよい。保護フィルムを剥離した後、工程S2で用いる減圧容器の内部に粘着層付き透明面材を移送するまでの間、粘着層付き透明面材を大気中に晒すことなく、減圧雰囲気下に保管できるのであれば、保護フィルムの剥離を減圧雰囲気下で実施することが好ましい。
ただし、生産設備等の都合上、保護フィルムの剥離を減圧雰囲気下で実施することは実際には困難であることが多い。その場合、保護フィルムの剥離を大気中で実施しても特に問題はない。保護フィルム剥離工程に減圧容器を準備する必要がない点では、保護フィルムの剥離を大気中で実施することが好ましい。保護フィルムの剥離後は、速やかに次の工程S2を行うことが好ましい。 (Step S1: Protective film peeling step)
In this step, the protective film is peeled from the transparent surface material with the adhesive layer, which is covered with the protective film. The protective film may be peeled in the air or in a reduced pressure atmosphere. After the protective film is peeled off, the transparent surface material with the adhesive layer can be stored in a reduced pressure atmosphere without being exposed to the atmosphere until the transparent surface material with the adhesive layer is transferred to the inside of the vacuum container used in the step S2. If it exists, it is preferable to carry out peeling of the protective film under a reduced pressure atmosphere.
However, it is often difficult to actually remove the protective film in a reduced pressure atmosphere due to production facilities and the like. In that case, there is no particular problem even if the protective film is peeled off in the air. It is preferable to carry out the peeling of the protective film in the air in that it is not necessary to prepare a vacuum container for the protective film peeling step. After the protective film is peeled off, it is preferable to immediately perform the next step S2.
(工程S2:貼合工程)
該工程では、貼合装置において、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねた状態で貼合する。このとき、貼合装置の減圧容器において、表示パネルと粘着層付き透明面材とを減圧雰囲気下で貼合することが好ましい。減圧雰囲気下で貼合を行うことにより、表示パネルと粘着層との界面に気泡が生じにくくなる。減圧容器の内部では、減圧雰囲気を所定時間保持した後、減圧雰囲気を解除して常圧とする。
貼合の際の減圧雰囲気は、20kPa以下が好ましく、15~0.5kPaがより好ましく、10~0.2kPaがさらに好ましい。減圧度が前記上限以下であれば、気泡が残存しにくく、下限以上であれば、大がかりな減圧装置が不要となる。 (Process S2: Pasting process)
In this process, in the bonding apparatus, the display panel and the transparent surface material with the adhesive layer are bonded together in a state where the adhesive layer is in contact with the display panel. At this time, in the decompression container of the pasting device, it is preferable to paste the display panel and the transparent surface material with the adhesive layer in a reduced pressure atmosphere. By performing bonding in a reduced pressure atmosphere, bubbles are less likely to be generated at the interface between the display panel and the adhesive layer. Inside the decompression vessel, after maintaining the decompressed atmosphere for a predetermined time, the decompressed atmosphere is released to normal pressure.
The reduced pressure atmosphere at the time of pasting is preferably 20 kPa or less, more preferably 15 to 0.5 kPa, and even more preferably 10 to 0.2 kPa. If the degree of decompression is less than or equal to the above upper limit, bubbles are unlikely to remain, and if the degree of decompression is greater than or equal to the lower limit, a large decompression device is not required.
該工程では、貼合装置において、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねた状態で貼合する。このとき、貼合装置の減圧容器において、表示パネルと粘着層付き透明面材とを減圧雰囲気下で貼合することが好ましい。減圧雰囲気下で貼合を行うことにより、表示パネルと粘着層との界面に気泡が生じにくくなる。減圧容器の内部では、減圧雰囲気を所定時間保持した後、減圧雰囲気を解除して常圧とする。
貼合の際の減圧雰囲気は、20kPa以下が好ましく、15~0.5kPaがより好ましく、10~0.2kPaがさらに好ましい。減圧度が前記上限以下であれば、気泡が残存しにくく、下限以上であれば、大がかりな減圧装置が不要となる。 (Process S2: Pasting process)
In this process, in the bonding apparatus, the display panel and the transparent surface material with the adhesive layer are bonded together in a state where the adhesive layer is in contact with the display panel. At this time, in the decompression container of the pasting device, it is preferable to paste the display panel and the transparent surface material with the adhesive layer in a reduced pressure atmosphere. By performing bonding in a reduced pressure atmosphere, bubbles are less likely to be generated at the interface between the display panel and the adhesive layer. Inside the decompression vessel, after maintaining the decompressed atmosphere for a predetermined time, the decompressed atmosphere is released to normal pressure.
The reduced pressure atmosphere at the time of pasting is preferably 20 kPa or less, more preferably 15 to 0.5 kPa, and even more preferably 10 to 0.2 kPa. If the degree of decompression is less than or equal to the above upper limit, bubbles are unlikely to remain, and if the degree of decompression is greater than or equal to the lower limit, a large decompression device is not required.
表示パネルと粘着層付き透明面材とを重ね合わせた時点から減圧雰囲気を解除するまでの時間は、生産効率の点から短時間である方が好ましい。たとえば1分以内が好ましく、10秒以内がより好ましい。
表示パネルと粘着層付き透明面材とを貼合した後に、硬化が不完全な粘着層に再び光を照射したり、加熱したりすることで粘着層の硬化を促進し、粘着層の硬化状態を安定化させてもよい。 From the point of production efficiency, it is preferable that the time from when the display panel and the transparent surface material with the adhesive layer are overlapped to when the reduced pressure atmosphere is released is short. For example, it is preferably within 1 minute, and more preferably within 10 seconds.
After bonding the display panel and the transparent face with adhesive layer, the adhesive layer that is not fully cured is irradiated with light again or heated to accelerate the curing of the adhesive layer, and the adhesive layer is cured. May be stabilized.
表示パネルと粘着層付き透明面材とを貼合した後に、硬化が不完全な粘着層に再び光を照射したり、加熱したりすることで粘着層の硬化を促進し、粘着層の硬化状態を安定化させてもよい。 From the point of production efficiency, it is preferable that the time from when the display panel and the transparent surface material with the adhesive layer are overlapped to when the reduced pressure atmosphere is released is short. For example, it is preferably within 1 minute, and more preferably within 10 seconds.
After bonding the display panel and the transparent face with adhesive layer, the adhesive layer that is not fully cured is irradiated with light again or heated to accelerate the curing of the adhesive layer, and the adhesive layer is cured. May be stabilized.
粘着層付き透明面材が可撓性を有する場合、粘着層付き透明面材の粘着層が形成された面側が凸になるように、粘着層付き透明面材を湾曲させた状態とし、粘着層付き透明面材を一端側から他端側に向けて徐々に表示パネルに重ね合わせる方法で貼合してもよい。該方法によれば、粘着層付き透明面材と表示パネルとの間の空間に存在する気体が一端側から他端側に押し出されながら貼合が行われるため、表示パネルと粘着層との界面に気泡が生じにくくなる。
When the transparent surface material with the adhesive layer has flexibility, the transparent surface material with the adhesive layer is curved so that the surface side on which the adhesive layer is formed of the transparent surface material with the adhesive layer is convex, and the adhesive layer The attached transparent surface material may be bonded by a method of gradually overlapping the display panel from one end side to the other end side. According to this method, since the gas existing in the space between the transparent surface material with the adhesive layer and the display panel is pushed out from one end side to the other end side, the bonding is performed, so the interface between the display panel and the adhesive layer Air bubbles are less likely to be generated.
(作用機序)
図12に示すように、粘着層付き透明面材2と表示パネル50とを貼合した直後には、表示パネル50と粘着層14との界面に、密閉された空間である気泡M1、M2が生じることがあるが、貼合直後に発生した気泡M1、M2のほとんどは所定時間経過後、消滅する。
本発明者らは、貼合直後に発生した気泡が消滅するメカニズムを、以下のように推察した。気泡の体積が縮小していく過程には、P1、P2、P3の3つのプロセスが考えられる。 (Mechanism of action)
As shown in FIG. 12, immediately after bonding thetransparent surface material 2 with the adhesive layer and the display panel 50, bubbles M1 and M2, which are sealed spaces, are formed at the interface between the display panel 50 and the adhesive layer 14. Although it may occur, most of the bubbles M1 and M2 generated immediately after bonding disappear after a predetermined time.
The present inventors inferred the mechanism of disappearance of bubbles generated immediately after bonding as follows. Three processes of P1, P2, and P3 can be considered as the process of reducing the volume of the bubbles.
図12に示すように、粘着層付き透明面材2と表示パネル50とを貼合した直後には、表示パネル50と粘着層14との界面に、密閉された空間である気泡M1、M2が生じることがあるが、貼合直後に発生した気泡M1、M2のほとんどは所定時間経過後、消滅する。
本発明者らは、貼合直後に発生した気泡が消滅するメカニズムを、以下のように推察した。気泡の体積が縮小していく過程には、P1、P2、P3の3つのプロセスが考えられる。 (Mechanism of action)
As shown in FIG. 12, immediately after bonding the
The present inventors inferred the mechanism of disappearance of bubbles generated immediately after bonding as follows. Three processes of P1, P2, and P3 can be considered as the process of reducing the volume of the bubbles.
(プロセスP1:貼合差圧による体積縮小)
プロセスP1は、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを貼合した後、常圧雰囲気下に戻したときに、減圧状態にある気泡内の圧力と、粘着層に外部から加わる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧が生じ、この差圧によって気泡の体積が減少する過程である。プロセスP1の期間は、たとえば数秒程度である。すなわち、圧力を常圧雰囲気に戻した時点から数秒後には気泡の体積は急激に縮小する。 (Process P1: Volume reduction by bonding differential pressure)
In the process P1, after the display panel and the transparent surface material with the adhesive layer are bonded in a reduced pressure atmosphere, when the pressure is returned to the normal pressure atmosphere, the pressure inside the bubbles in the reduced pressure state and the adhesive layer from the outside This is a process in which a differential pressure from the applied pressure (that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere) is generated, and the volume of the bubbles is reduced by this differential pressure. The period of the process P1 is, for example, about several seconds. That is, the volume of the bubble is rapidly reduced after a few seconds from the time when the pressure is returned to the atmospheric pressure.
プロセスP1は、減圧雰囲気下にて表示パネルと粘着層付き透明面材とを貼合した後、常圧雰囲気下に戻したときに、減圧状態にある気泡内の圧力と、粘着層に外部から加わる圧力(すなわち、大気圧雰囲気下に戻した際の大気圧)との差圧が生じ、この差圧によって気泡の体積が減少する過程である。プロセスP1の期間は、たとえば数秒程度である。すなわち、圧力を常圧雰囲気に戻した時点から数秒後には気泡の体積は急激に縮小する。 (Process P1: Volume reduction by bonding differential pressure)
In the process P1, after the display panel and the transparent surface material with the adhesive layer are bonded in a reduced pressure atmosphere, when the pressure is returned to the normal pressure atmosphere, the pressure inside the bubbles in the reduced pressure state and the adhesive layer from the outside This is a process in which a differential pressure from the applied pressure (that is, the atmospheric pressure when returned to the atmospheric pressure atmosphere) is generated, and the volume of the bubbles is reduced by this differential pressure. The period of the process P1 is, for example, about several seconds. That is, the volume of the bubble is rapidly reduced after a few seconds from the time when the pressure is returned to the atmospheric pressure.
(プロセスP2:気泡内気体の粘着層への吸収による体積縮小)
プロセスP2は、気泡内に閉じこめられた気体が気泡と接する粘着層に吸収され、溶解することにより、気泡の体積が減少する過程である。プロセスP2の期間は、たとえば数分~数10分程度である。プロセスP2における気泡の体積縮小の速度は、プロセスP1における気泡の体積縮小の速度よりも遅い。 (Process P2: Volume reduction by absorption of gas in bubbles into the adhesive layer)
Process P2 is a process in which the volume of bubbles is reduced by the gas confined in the bubbles being absorbed and dissolved in the adhesive layer in contact with the bubbles. The period of the process P2 is about several minutes to several tens of minutes, for example. The rate of bubble volume reduction in process P2 is slower than the rate of bubble volume reduction in process P1.
プロセスP2は、気泡内に閉じこめられた気体が気泡と接する粘着層に吸収され、溶解することにより、気泡の体積が減少する過程である。プロセスP2の期間は、たとえば数分~数10分程度である。プロセスP2における気泡の体積縮小の速度は、プロセスP1における気泡の体積縮小の速度よりも遅い。 (Process P2: Volume reduction by absorption of gas in bubbles into the adhesive layer)
Process P2 is a process in which the volume of bubbles is reduced by the gas confined in the bubbles being absorbed and dissolved in the adhesive layer in contact with the bubbles. The period of the process P2 is about several minutes to several tens of minutes, for example. The rate of bubble volume reduction in process P2 is slower than the rate of bubble volume reduction in process P1.
(プロセスP3:粘着層内での気体の拡散による体積縮小)
プロセスP3は、プロセスP2において粘着層に溶解した気体が気泡の周囲からその外側に拡散するのに伴って、気泡内の気体が気泡と接する粘着層に再吸収され、再溶解することにより、気泡の体積が減少する過程である。
すなわち、プロセスP2を経て気泡内に残存する気体濃度と気泡周囲の粘着層に溶解した気体濃度とがほぼ平衡状態となる。ところが、今度は、気泡周囲の粘着層に溶解した気体濃度と気泡から離れた位置の粘着層中の気体濃度とが非平衡状態となるため、粘着層に溶解した気体が気泡の周囲からさらにその外側に拡散していく。
この過程を経て、気泡内の気体が気泡と接する粘着層に再吸収され、再溶解する。プロセスP3の期間は、たとえば数時間以上である。プロセスP3における気泡の体積縮小の速度は、粘着層内の気体の拡散速度に依るため、プロセスP2における気泡の体積縮小の速度よりもさらに遅い。プロセスP3を経て気泡はほぼ完全に消滅する。 (Process P3: Volume reduction due to gas diffusion in the adhesive layer)
In the process P3, as the gas dissolved in the adhesive layer in the process P2 diffuses from the periphery of the bubble to the outside thereof, the gas in the bubble is reabsorbed by the adhesive layer in contact with the bubble and is dissolved again. This is a process of decreasing the volume of the.
That is, the gas concentration remaining in the bubbles after the process P2 and the gas concentration dissolved in the adhesive layer around the bubbles are almost in equilibrium. However, this time, since the gas concentration dissolved in the adhesive layer around the bubble and the gas concentration in the adhesive layer located away from the bubble are in a non-equilibrium state, the gas dissolved in the adhesive layer is further increased from the periphery of the bubble. It spreads outside.
Through this process, the gas in the bubbles is reabsorbed and re-dissolved in the adhesive layer in contact with the bubbles. The period of the process P3 is, for example, several hours or more. The speed of the bubble volume reduction in the process P3 depends on the diffusion rate of the gas in the adhesive layer, and is therefore slower than the speed of the bubble volume reduction in the process P2. The bubbles disappear almost completely through the process P3.
プロセスP3は、プロセスP2において粘着層に溶解した気体が気泡の周囲からその外側に拡散するのに伴って、気泡内の気体が気泡と接する粘着層に再吸収され、再溶解することにより、気泡の体積が減少する過程である。
すなわち、プロセスP2を経て気泡内に残存する気体濃度と気泡周囲の粘着層に溶解した気体濃度とがほぼ平衡状態となる。ところが、今度は、気泡周囲の粘着層に溶解した気体濃度と気泡から離れた位置の粘着層中の気体濃度とが非平衡状態となるため、粘着層に溶解した気体が気泡の周囲からさらにその外側に拡散していく。
この過程を経て、気泡内の気体が気泡と接する粘着層に再吸収され、再溶解する。プロセスP3の期間は、たとえば数時間以上である。プロセスP3における気泡の体積縮小の速度は、粘着層内の気体の拡散速度に依るため、プロセスP2における気泡の体積縮小の速度よりもさらに遅い。プロセスP3を経て気泡はほぼ完全に消滅する。 (Process P3: Volume reduction due to gas diffusion in the adhesive layer)
In the process P3, as the gas dissolved in the adhesive layer in the process P2 diffuses from the periphery of the bubble to the outside thereof, the gas in the bubble is reabsorbed by the adhesive layer in contact with the bubble and is dissolved again. This is a process of decreasing the volume of the.
That is, the gas concentration remaining in the bubbles after the process P2 and the gas concentration dissolved in the adhesive layer around the bubbles are almost in equilibrium. However, this time, since the gas concentration dissolved in the adhesive layer around the bubble and the gas concentration in the adhesive layer located away from the bubble are in a non-equilibrium state, the gas dissolved in the adhesive layer is further increased from the periphery of the bubble. It spreads outside.
Through this process, the gas in the bubbles is reabsorbed and re-dissolved in the adhesive layer in contact with the bubbles. The period of the process P3 is, for example, several hours or more. The speed of the bubble volume reduction in the process P3 depends on the diffusion rate of the gas in the adhesive layer, and is therefore slower than the speed of the bubble volume reduction in the process P2. The bubbles disappear almost completely through the process P3.
上述したように、粘着層付き透明面材2と表示パネル50とを貼合した直後には、表示パネル50と粘着層14との界面に気泡(図12のM1、M2)が生じる。
本発明者らの検討の結果、従来の粘着層付き透明面材では、製造後、長期間保管した場合に、気泡消滅に長時間を要する傾向があることがわかったが、本発明の粘着層付き透明面材によれば、製造されてから長期間が経過した後に被貼合体との貼合に使用した場合でも、気泡は短時間で消滅する。 As described above, immediately after thetransparent surface material 2 with the adhesive layer 2 and the display panel 50 are bonded together, bubbles (M1 and M2 in FIG. 12) are generated at the interface between the display panel 50 and the adhesive layer 14.
As a result of the study by the present inventors, it has been found that the conventional transparent surface material with an adhesive layer tends to require a long time for the disappearance of bubbles when stored for a long time after production. According to the attached transparent face material, the bubbles disappear in a short time even when used for pasting with an object to be pasted after a long period of time has passed since the manufacture.
本発明者らの検討の結果、従来の粘着層付き透明面材では、製造後、長期間保管した場合に、気泡消滅に長時間を要する傾向があることがわかったが、本発明の粘着層付き透明面材によれば、製造されてから長期間が経過した後に被貼合体との貼合に使用した場合でも、気泡は短時間で消滅する。 As described above, immediately after the
As a result of the study by the present inventors, it has been found that the conventional transparent surface material with an adhesive layer tends to require a long time for the disappearance of bubbles when stored for a long time after production. According to the attached transparent face material, the bubbles disappear in a short time even when used for pasting with an object to be pasted after a long period of time has passed since the manufacture.
本発明の粘着層付き透明面材を用いた場合に気泡が短時間で消滅する理由については、以下のように推察できる。
上述したように、本発明の粘着層付き透明面材は、粘着層中の水酸基の濃度が、600×10-6モル/g以下であり、粘着層中のウレタン結合の濃度が、150×10-6モル/g以下である。そのため、該粘着層は、凝集力が弱く、粘着層中への気体の拡散がしやすくなっている。これによって、プロセスP2、P3が速まり、結果として残存する気泡が短時間で消滅する。 The reason why the bubbles disappear in a short time when the transparent surface material with an adhesive layer of the present invention is used can be inferred as follows.
As described above, the adhesive layer with transparent surface material of the present invention, the concentration of hydroxyl groups in the adhesive layer is not more than 600 × 10 -6 mol / g, the concentration of urethane linkages in the adhesive layer, 0.99 × 10 -6 mol / g or less. Therefore, the pressure-sensitive adhesive layer has a weak cohesive force and facilitates gas diffusion into the pressure-sensitive adhesive layer. As a result, the processes P2 and P3 are accelerated, and as a result, the remaining bubbles disappear in a short time.
上述したように、本発明の粘着層付き透明面材は、粘着層中の水酸基の濃度が、600×10-6モル/g以下であり、粘着層中のウレタン結合の濃度が、150×10-6モル/g以下である。そのため、該粘着層は、凝集力が弱く、粘着層中への気体の拡散がしやすくなっている。これによって、プロセスP2、P3が速まり、結果として残存する気泡が短時間で消滅する。 The reason why the bubbles disappear in a short time when the transparent surface material with an adhesive layer of the present invention is used can be inferred as follows.
As described above, the adhesive layer with transparent surface material of the present invention, the concentration of hydroxyl groups in the adhesive layer is not more than 600 × 10 -6 mol / g, the concentration of urethane linkages in the adhesive layer, 0.99 × 10 -6 mol / g or less. Therefore, the pressure-sensitive adhesive layer has a weak cohesive force and facilitates gas diffusion into the pressure-sensitive adhesive layer. As a result, the processes P2 and P3 are accelerated, and as a result, the remaining bubbles disappear in a short time.
(他の実施形態)
本発明の表示装置の製造方法は、本発明の表示装置を製造する方法であって、減圧雰囲気下にて、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねて貼合する方法であればよく、上述した製造方法に限定はされない。
たとえば、上述した製造方法では、第2の実施形態の粘着層付き透明面材の製造工程において粘着層が減圧条件に置かれることによって、粘着層の気体含有量が少なくなるが、減圧下に置かれることにより粘着層の気体含有量が少なくなる工程は、粘着層付き透明面材を被貼合物に貼合せる工程の前であれば、いずれの時点であってもよい。 (Other embodiments)
The manufacturing method of the display device of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are brought into contact with the display panel in a reduced pressure atmosphere. Any method can be used as long as it is laminated and bonded, and the production method described above is not limited.
For example, in the manufacturing method described above, the gas content of the adhesive layer is reduced by placing the adhesive layer under reduced pressure conditions in the manufacturing process of the transparent face material with the adhesive layer of the second embodiment. As long as it is before the process of bonding the transparent surface material with an adhesion layer to a to-be-bonded thing, the process by which the gas content of the adhesion layer decreases may be any time.
本発明の表示装置の製造方法は、本発明の表示装置を製造する方法であって、減圧雰囲気下にて、表示パネルと粘着層付き透明面材とを、粘着層が表示パネルに接するように重ねて貼合する方法であればよく、上述した製造方法に限定はされない。
たとえば、上述した製造方法では、第2の実施形態の粘着層付き透明面材の製造工程において粘着層が減圧条件に置かれることによって、粘着層の気体含有量が少なくなるが、減圧下に置かれることにより粘着層の気体含有量が少なくなる工程は、粘着層付き透明面材を被貼合物に貼合せる工程の前であれば、いずれの時点であってもよい。 (Other embodiments)
The manufacturing method of the display device of the present invention is a method of manufacturing the display device of the present invention, wherein the display panel and the transparent surface material with the adhesive layer are brought into contact with the display panel in a reduced pressure atmosphere. Any method can be used as long as it is laminated and bonded, and the production method described above is not limited.
For example, in the manufacturing method described above, the gas content of the adhesive layer is reduced by placing the adhesive layer under reduced pressure conditions in the manufacturing process of the transparent face material with the adhesive layer of the second embodiment. As long as it is before the process of bonding the transparent surface material with an adhesion layer to a to-be-bonded thing, the process by which the gas content of the adhesion layer decreases may be any time.
また、本発明の趣旨を逸脱しない範囲において種々の変更を加えることができる。
たとえば、粘着層付き透明面材は、タッチパネル等の座標入力装置に貼合してもよい。
また、透明面材は、タッチパネル付き表示装置における、タッチパネル部分を構成する透明電極付き基板であってもよい。透明電極付き基板の両面に粘着層を形成することもでき、透明面材と表示パネルとを、両面に粘着層を形成した透明電極付き基板を介して貼合することもできる。 Various modifications can be made without departing from the spirit of the present invention.
For example, the transparent surface material with an adhesive layer may be bonded to a coordinate input device such as a touch panel.
The transparent surface material may be a substrate with a transparent electrode that constitutes a touch panel portion in a display device with a touch panel. An adhesive layer can also be formed on both surfaces of a substrate with a transparent electrode, and a transparent surface material and a display panel can be bonded via a substrate with a transparent electrode having an adhesive layer formed on both surfaces.
たとえば、粘着層付き透明面材は、タッチパネル等の座標入力装置に貼合してもよい。
また、透明面材は、タッチパネル付き表示装置における、タッチパネル部分を構成する透明電極付き基板であってもよい。透明電極付き基板の両面に粘着層を形成することもでき、透明面材と表示パネルとを、両面に粘着層を形成した透明電極付き基板を介して貼合することもできる。 Various modifications can be made without departing from the spirit of the present invention.
For example, the transparent surface material with an adhesive layer may be bonded to a coordinate input device such as a touch panel.
The transparent surface material may be a substrate with a transparent electrode that constitutes a touch panel portion in a display device with a touch panel. An adhesive layer can also be formed on both surfaces of a substrate with a transparent electrode, and a transparent surface material and a display panel can be bonded via a substrate with a transparent electrode having an adhesive layer formed on both surfaces.
<粘着シート>
本発明の粘着シートは、粘着シート形成用硬化性樹脂組成物の硬化物からなる。
本発明の粘着シートは、必要に応じて、粘着シートの一方の表面または両面に、剥離可能な保護フィルムをさらに有する保護フィルム付き粘着シートであってもよい。 <Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention comprises a cured product of a curable resin composition for forming a pressure-sensitive adhesive sheet.
The pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet with a protective film further having a peelable protective film on one surface or both surfaces of the pressure-sensitive adhesive sheet, if necessary.
本発明の粘着シートは、粘着シート形成用硬化性樹脂組成物の硬化物からなる。
本発明の粘着シートは、必要に応じて、粘着シートの一方の表面または両面に、剥離可能な保護フィルムをさらに有する保護フィルム付き粘着シートであってもよい。 <Adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention comprises a cured product of a curable resin composition for forming a pressure-sensitive adhesive sheet.
The pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet with a protective film further having a peelable protective film on one surface or both surfaces of the pressure-sensitive adhesive sheet, if necessary.
粘着シートは、上述した粘着層付き透明面材における粘着層を透明面材なしで単独で存在させたものである。よって、粘着シートの特性および材料、ならびに好ましい態様は、上述した粘着層と同様であり、詳細な説明は省略する。
The pressure-sensitive adhesive sheet is obtained by allowing the pressure-sensitive adhesive layer in the above-described transparent surface material with a pressure-sensitive adhesive layer to exist alone without the transparent surface material. Therefore, the characteristics and material of the pressure-sensitive adhesive sheet, and preferred embodiments are the same as those of the pressure-sensitive adhesive layer described above, and detailed description thereof is omitted.
粘着シートは、たとえば、透明面材の代わりに保護フィルム、または保護フィルム付き支持面材を用いることによって、粘着層付き透明面材の製造方法と同様の製造方法によって製造できる。
The pressure-sensitive adhesive sheet can be produced by a production method similar to the production method of the transparent surface material with an adhesive layer, for example, by using a protective film or a support surface material with a protective film instead of the transparent surface material.
以上説明した本発明の粘着シートにあっては、粘着シート層中の水酸基の濃度が、600×10-6モル/g以下であり、粘着シート中のウレタン結合の濃度が、150×10-6モル/g以下であるため、被貼合物(透明面材、表示パネル等)と貼合した際に、被貼合物と粘着シートとの界面に残存する気泡が迅速に消滅し得る。また、粘着シート中の水酸基の濃度が、100×10-6モル/g以上であるため、粘着シートと被貼合物(たとえば、透明面材、表示パネル等)との密着性が良好となる。
In the pressure-sensitive adhesive sheet of the present invention described above, the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet layer is 600 × 10 −6 mol / g or less, and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is 150 × 10 −6. Since it is mol / g or less, when it bonds with a to-be-bonded object (transparent surface material, a display panel, etc.), the bubble which remain | survives in the interface of a to-be-bonded object and an adhesive sheet can lose | disappear rapidly. Moreover, since the concentration of the hydroxyl group in the pressure-sensitive adhesive sheet is 100 × 10 −6 mol / g or more, the adhesion between the pressure-sensitive adhesive sheet and the object to be bonded (for example, a transparent surface material, a display panel, etc.) becomes good. .
以下に、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの例によって限定されない。
例1、2、4、5は実施例であり、例3、6は比較例である。
各例における透明面材、被貼合物、保護フィルム付き支持面材、硬化性オリゴマー(A)、非硬化性オリゴマー(C)、第一組成物、第二組成物は、以下の通りに作製したものである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Examples 1, 2, 4, and 5 are examples, and examples 3 and 6 are comparative examples.
The transparent surface material, the object to be bonded, the support surface material with a protective film, the curable oligomer (A), the non-curable oligomer (C), the first composition, and the second composition in each example are prepared as follows. It is a thing.
例1、2、4、5は実施例であり、例3、6は比較例である。
各例における透明面材、被貼合物、保護フィルム付き支持面材、硬化性オリゴマー(A)、非硬化性オリゴマー(C)、第一組成物、第二組成物は、以下の通りに作製したものである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Examples 1, 2, 4, and 5 are examples, and examples 3 and 6 are comparative examples.
The transparent surface material, the object to be bonded, the support surface material with a protective film, the curable oligomer (A), the non-curable oligomer (C), the first composition, and the second composition in each example are prepared as follows. It is a thing.
(透明面材)
透明面材(1):
長さ240mm、幅190mm、厚さ1.3mmのソーダライムガラス板の一方の表面の周縁部に、透光部が長さ218mm、幅168mmとなるように黒色顔料を含むインクによる印刷にて額縁状に遮光印刷部を形成して、透明面材(1)を作製した。 (Transparent surface material)
Transparent face material (1):
Printed with ink containing a black pigment so that the translucent portion is 218 mm long and 168 mm wide at the periphery of one surface of a soda-lime glass plate having a length of 240 mm, a width of 190 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (1).
透明面材(1):
長さ240mm、幅190mm、厚さ1.3mmのソーダライムガラス板の一方の表面の周縁部に、透光部が長さ218mm、幅168mmとなるように黒色顔料を含むインクによる印刷にて額縁状に遮光印刷部を形成して、透明面材(1)を作製した。 (Transparent surface material)
Transparent face material (1):
Printed with ink containing a black pigment so that the translucent portion is 218 mm long and 168 mm wide at the periphery of one surface of a soda-lime glass plate having a length of 240 mm, a width of 190 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (1).
透明面材(2):
長さ100mm、幅100mm、厚さ1.3mmのソーダライムガラス板の一方の表面の周縁部に、透光部が長さ85mm、幅85mmとなるように黒色顔料を含むインクによる印刷にて額縁状に遮光印刷部を形成して、透明面材(2)を作製した。 Transparent face material (2):
Printed with ink containing a black pigment so that the translucent portion is 85 mm long and 85 mm wide on one surface of a soda lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (2).
長さ100mm、幅100mm、厚さ1.3mmのソーダライムガラス板の一方の表面の周縁部に、透光部が長さ85mm、幅85mmとなるように黒色顔料を含むインクによる印刷にて額縁状に遮光印刷部を形成して、透明面材(2)を作製した。 Transparent face material (2):
Printed with ink containing a black pigment so that the translucent portion is 85 mm long and 85 mm wide on one surface of a soda lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 1.3 mm A light shielding printing part was formed in a shape to produce a transparent surface material (2).
(被貼合物)
被貼合物(1):
長さ220mm、幅170mm、厚さ1.1mmのソーダライムガラス板の一方の面に、粘着層付き偏光板(ポラテクノ社製、KN-18240T)を貼合して、液晶パネルを代用する被貼合物(1)とした。 (To be bonded)
Article to be bonded (1):
A polarizing plate with an adhesive layer (Polatechno Co., Ltd., KN-18240T) is bonded to one surface of a soda lime glass plate having a length of 220 mm, a width of 170 mm, and a thickness of 1.1 mm, and a liquid crystal panel is substituted. Compound (1) was obtained.
被貼合物(1):
長さ220mm、幅170mm、厚さ1.1mmのソーダライムガラス板の一方の面に、粘着層付き偏光板(ポラテクノ社製、KN-18240T)を貼合して、液晶パネルを代用する被貼合物(1)とした。 (To be bonded)
Article to be bonded (1):
A polarizing plate with an adhesive layer (Polatechno Co., Ltd., KN-18240T) is bonded to one surface of a soda lime glass plate having a length of 220 mm, a width of 170 mm, and a thickness of 1.1 mm, and a liquid crystal panel is substituted. Compound (1) was obtained.
被貼合物(2):
長さ90mm、幅90mm、厚さ2mmのソーダライムガラス板の一方の面に、粘着層付き偏光板(ポラテクノ社製、KN-18240T)を貼合して、液晶表示パネルを代用する被貼合物(2)とした。 Article to be bonded (2):
Adhesive layered polarizing plate (Polatechno KN-18240T) is bonded to one side of a soda lime glass plate with a length of 90 mm, a width of 90 mm, and a thickness of 2 mm. It was set as thing (2).
長さ90mm、幅90mm、厚さ2mmのソーダライムガラス板の一方の面に、粘着層付き偏光板(ポラテクノ社製、KN-18240T)を貼合して、液晶表示パネルを代用する被貼合物(2)とした。 Article to be bonded (2):
Adhesive layered polarizing plate (Polatechno KN-18240T) is bonded to one side of a soda lime glass plate with a length of 90 mm, a width of 90 mm, and a thickness of 2 mm. It was set as thing (2).
(保護フィルム付き支持面材)
長さ100mm、幅100mm、厚さ2mmのソーダライムガラス板からなる支持面材の一方の面に、長さ130mm、幅130mm、厚さ0.75mmの保護フィルム(三井化学東セロ社製、ピュアテクト(登録商標)VLH-9)を、保護フィルムの粘着面がガラスに接するようにゴムロールを用いて貼合し、保護フィルム付き支持面材を作製した。 (Support surface with protective film)
A protective film (manufactured by Mitsui Chemicals Tosero Co., Ltd., Puretect) on one side of a support surface material made of a soda-lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm. (Registered Trademark) VLH-9) was bonded using a rubber roll so that the adhesive surface of the protective film was in contact with the glass to produce a support surface material with a protective film.
長さ100mm、幅100mm、厚さ2mmのソーダライムガラス板からなる支持面材の一方の面に、長さ130mm、幅130mm、厚さ0.75mmの保護フィルム(三井化学東セロ社製、ピュアテクト(登録商標)VLH-9)を、保護フィルムの粘着面がガラスに接するようにゴムロールを用いて貼合し、保護フィルム付き支持面材を作製した。 (Support surface with protective film)
A protective film (manufactured by Mitsui Chemicals Tosero Co., Ltd., Puretect) on one side of a support surface material made of a soda-lime glass plate having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm. (Registered Trademark) VLH-9) was bonded using a rubber roll so that the adhesive surface of the protective film was in contact with the glass to produce a support surface material with a protective film.
(硬化性オリゴマー(A))
UA-1:
2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:18000)と、イソホロンジイソシアネートとを、4対5となるモル比で混合し、錫化合物の触媒存在下で、70℃で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートを、プレポリマーと2-ヒドロキシエチルアクリレートとがほぼ1対2となるモル比で加えて70℃で反応させることによって、ウレタンアクリレートオリゴマー(以下、UA-1と記す。)を得た。
UA-1の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約73000であり、25℃における粘度は、約250Pa・sであった。 (Curable oligomer (A))
UA-1:
Bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 18000) and isophorone diisocyanate are mixed at a molar ratio of 4 to 5, and obtained by reacting at 70 ° C. in the presence of a tin compound catalyst. 2-hydroxyethyl acrylate was added to the resulting prepolymer at a molar ratio of prepolymer and 2-hydroxyethyl acrylate of approximately 1: 2, and reacted at 70 ° C. to obtain a urethane acrylate oligomer (hereinafter referred to as UA-). 1)).
The average number of addition polymerizable unsaturated double bonds of UA-1 was 2, the number average molecular weight was about 73,000, and the viscosity at 25 ° C. was about 250 Pa · s.
UA-1:
2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:18000)と、イソホロンジイソシアネートとを、4対5となるモル比で混合し、錫化合物の触媒存在下で、70℃で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートを、プレポリマーと2-ヒドロキシエチルアクリレートとがほぼ1対2となるモル比で加えて70℃で反応させることによって、ウレタンアクリレートオリゴマー(以下、UA-1と記す。)を得た。
UA-1の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約73000であり、25℃における粘度は、約250Pa・sであった。 (Curable oligomer (A))
UA-1:
Bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 18000) and isophorone diisocyanate are mixed at a molar ratio of 4 to 5, and obtained by reacting at 70 ° C. in the presence of a tin compound catalyst. 2-hydroxyethyl acrylate was added to the resulting prepolymer at a molar ratio of prepolymer and 2-hydroxyethyl acrylate of approximately 1: 2, and reacted at 70 ° C. to obtain a urethane acrylate oligomer (hereinafter referred to as UA-). 1)).
The average number of addition polymerizable unsaturated double bonds of UA-1 was 2, the number average molecular weight was about 73,000, and the viscosity at 25 ° C. was about 250 Pa · s.
UA-2:
2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:10000)を用いた以外は、UA-1と同様の方法でウレタンアクリレートオリゴマー(以下、UA-2と記す。)を得た。
UA-2の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約41000であり、25℃における粘度は、約250Pa・sであった。 UA-2:
A urethane acrylate oligomer (hereinafter referred to as UA-2) was obtained in the same manner as UA-1, except that bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) was used.
The average number of addition polymerizable unsaturated double bonds of UA-2 was 2, the number average molecular weight was about 41,000, and the viscosity at 25 ° C. was about 250 Pa · s.
2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:10000)を用いた以外は、UA-1と同様の方法でウレタンアクリレートオリゴマー(以下、UA-2と記す。)を得た。
UA-2の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約41000であり、25℃における粘度は、約250Pa・sであった。 UA-2:
A urethane acrylate oligomer (hereinafter referred to as UA-2) was obtained in the same manner as UA-1, except that bifunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) was used.
The average number of addition polymerizable unsaturated double bonds of UA-2 was 2, the number average molecular weight was about 41,000, and the viscosity at 25 ° C. was about 250 Pa · s.
UA-3:
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)を用いた以外は、UA-1と同様の方法でウレタンアクリレートオリゴマー(以下、UA-3と記す。)を得た。
UA-3の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約17300であり、25℃における粘度は、約250Pa・sであった。 UA-3:
A urethane acrylate oligomer (hereinafter referred to as UA-3) is produced in the same manner as UA-1, except that a bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) is used. )
The average number of addition polymerizable unsaturated double bonds of UA-3 was 2, the number average molecular weight was about 17,300, and the viscosity at 25 ° C. was about 250 Pa · s.
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)を用いた以外は、UA-1と同様の方法でウレタンアクリレートオリゴマー(以下、UA-3と記す。)を得た。
UA-3の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、約17300であり、25℃における粘度は、約250Pa・sであった。 UA-3:
A urethane acrylate oligomer (hereinafter referred to as UA-3) is produced in the same manner as UA-1, except that a bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) is used. )
The average number of addition polymerizable unsaturated double bonds of UA-3 was 2, the number average molecular weight was about 17,300, and the viscosity at 25 ° C. was about 250 Pa · s.
UA-4:
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、ヘキサメチレンジイソシアネートとをモル比6:7で混合し、ついでイソボルニルアクリレート(大阪有機化学工業社製、IBXA)で希釈した後、錫触媒の存在下で、70℃で反応させてプレポリマーを得た。得られたプレポリマーに、2-ヒドロキシエチルアクリレートをプレポリマーと2-ヒドロキシエチルアクリレートがモル比で1:2となるように加えて70℃で反応させ、30質量%のイソボルニルアクリレートで希釈されたウレタンアクリレートオリゴマー(UA-4)(以下、UA-4と記す。)を得た。
UA-4の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、55000であり、60℃における粘度は、580Pa・sであった。 UA-4:
Bifunctional polypropylene glycol whose molecular terminal is modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and hexamethylene diisocyanate are mixed at a molar ratio of 6: 7, and then isobornyl acrylate (Osaka Organic Chemical Industry) After dilution with IBXA, a prepolymer was obtained by reaction at 70 ° C. in the presence of a tin catalyst. To the obtained prepolymer, 2-hydroxyethyl acrylate was added so that the molar ratio of the prepolymer and 2-hydroxyethyl acrylate was 1: 2, reacted at 70 ° C., and diluted with 30% by mass of isobornyl acrylate. A urethane acrylate oligomer (UA-4) (hereinafter referred to as UA-4) was obtained.
The average number of addition polymerizable unsaturated double bonds of UA-4 was 2, the number average molecular weight was 55000, and the viscosity at 60 ° C. was 580 Pa · s.
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、ヘキサメチレンジイソシアネートとをモル比6:7で混合し、ついでイソボルニルアクリレート(大阪有機化学工業社製、IBXA)で希釈した後、錫触媒の存在下で、70℃で反応させてプレポリマーを得た。得られたプレポリマーに、2-ヒドロキシエチルアクリレートをプレポリマーと2-ヒドロキシエチルアクリレートがモル比で1:2となるように加えて70℃で反応させ、30質量%のイソボルニルアクリレートで希釈されたウレタンアクリレートオリゴマー(UA-4)(以下、UA-4と記す。)を得た。
UA-4の付加重合性不飽和二重結合の平均数は2であり、数平均分子量は、55000であり、60℃における粘度は、580Pa・sであった。 UA-4:
Bifunctional polypropylene glycol whose molecular terminal is modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and hexamethylene diisocyanate are mixed at a molar ratio of 6: 7, and then isobornyl acrylate (Osaka Organic Chemical Industry) After dilution with IBXA, a prepolymer was obtained by reaction at 70 ° C. in the presence of a tin catalyst. To the obtained prepolymer, 2-hydroxyethyl acrylate was added so that the molar ratio of the prepolymer and 2-hydroxyethyl acrylate was 1: 2, reacted at 70 ° C., and diluted with 30% by mass of isobornyl acrylate. A urethane acrylate oligomer (UA-4) (hereinafter referred to as UA-4) was obtained.
The average number of addition polymerizable unsaturated double bonds of UA-4 was 2, the number average molecular weight was 55000, and the viscosity at 60 ° C. was 580 Pa · s.
UA-5:
1官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:10000)と、2-アクリロイルオキシエチルイソシアナートとを、1対1となるモル比で混合し、錫化合物の触媒存在下で、70℃で反応させてウレタンアクリレートオリゴマー(以下、UA-5と記す。)を得た。
UA-5の付加重合性不飽和二重結合の平均数は1であり、数平均分子量は、約10100であり、25℃における粘度は、約7Pa・sであった。 UA-5:
Monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) and 2-acryloyloxyethyl isocyanate are mixed at a molar ratio of 1: 1, and in the presence of a tin compound catalyst, 70 ° C. To obtain a urethane acrylate oligomer (hereinafter referred to as UA-5).
The average number of addition polymerizable unsaturated double bonds of UA-5 was 1, the number average molecular weight was about 10100, and the viscosity at 25 ° C. was about 7 Pa · s.
1官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:10000)と、2-アクリロイルオキシエチルイソシアナートとを、1対1となるモル比で混合し、錫化合物の触媒存在下で、70℃で反応させてウレタンアクリレートオリゴマー(以下、UA-5と記す。)を得た。
UA-5の付加重合性不飽和二重結合の平均数は1であり、数平均分子量は、約10100であり、25℃における粘度は、約7Pa・sであった。 UA-5:
Monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 10,000) and 2-acryloyloxyethyl isocyanate are mixed at a molar ratio of 1: 1, and in the presence of a tin compound catalyst, 70 ° C. To obtain a urethane acrylate oligomer (hereinafter referred to as UA-5).
The average number of addition polymerizable unsaturated double bonds of UA-5 was 1, the number average molecular weight was about 10100, and the viscosity at 25 ° C. was about 7 Pa · s.
UA-6:
1官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:5000)を用いた以外はUA-3と同様の方法でウレタンアクリレートオリゴマー(以下、UA-6と記す。)を得た。
UA-6の硬化性基数は1であり、数平均分子量は、約5100であり、25℃における粘度は、約3Pa・sであった。 UA-6:
A urethane acrylate oligomer (hereinafter referred to as UA-6) was obtained in the same manner as UA-3, except that monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 5000) was used.
The number of curable groups of UA-6 was 1, the number average molecular weight was about 5100, and the viscosity at 25 ° C. was about 3 Pa · s.
1官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:5000)を用いた以外はUA-3と同様の方法でウレタンアクリレートオリゴマー(以下、UA-6と記す。)を得た。
UA-6の硬化性基数は1であり、数平均分子量は、約5100であり、25℃における粘度は、約3Pa・sであった。 UA-6:
A urethane acrylate oligomer (hereinafter referred to as UA-6) was obtained in the same manner as UA-3, except that monofunctional polypropylene glycol (number average molecular weight calculated from hydroxyl value: 5000) was used.
The number of curable groups of UA-6 was 1, the number average molecular weight was about 5100, and the viscosity at 25 ° C. was about 3 Pa · s.
(非硬化性オリゴマー(C))
非硬化性オリゴマー(1):
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と分子末端をエチレンオキシドで変性した3官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:6200)を1対1の質量比で混合し、非硬化性オリゴマー(1)を得た。 (Non-curable oligomer (C))
Non-curable oligomer (1):
Bifunctional polypropylene glycol modified with ethylene oxide at the molecular end (number average molecular weight calculated from hydroxyl value: 4000) and trifunctional polypropylene glycol modified at molecular end with ethylene oxide (number average molecular weight calculated from hydroxyl value: 6200) The mixture was mixed at a mass ratio of 1: 1 to obtain a non-curable oligomer (1).
非硬化性オリゴマー(1):
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と分子末端をエチレンオキシドで変性した3官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:6200)を1対1の質量比で混合し、非硬化性オリゴマー(1)を得た。 (Non-curable oligomer (C))
Non-curable oligomer (1):
Bifunctional polypropylene glycol modified with ethylene oxide at the molecular end (number average molecular weight calculated from hydroxyl value: 4000) and trifunctional polypropylene glycol modified at molecular end with ethylene oxide (number average molecular weight calculated from hydroxyl value: 6200) The mixture was mixed at a mass ratio of 1: 1 to obtain a non-curable oligomer (1).
(第一組成物)
第一組成物(1):
(A)成分としてUA-1の20質量部、UA-5の32.5質量部、およびUA-6の32.5質量部、(B)成分としてフェニルグリシジルエーテルアクリレート(共栄社化学社製、エポキシエステル M-600A)の15質量部を均一に混合し、その後、該混合物の100質量部に、(D)成分としてビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させて混合し、その後、該混合物の100質量部に(C)成分として末端メチル化したポリプロピレングリコール(水酸基価より算出した数平均分子量:1200)の42.9質量部を均一に溶解させて混合し、第一組成物(1)を得た。
第一組成物(1)の25℃における粘度は、3.2Pa・sであった。第一組成物(1)中の水酸基の濃度は、471×10-6mol/g、ウレタン結合の濃度は、85×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、556×10-6mol/g、SP値は、18.2(J/cm3)1/2であった。水酸基、およびウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。
なお、水酸基の濃度の求め方は、(A)、(B)、(C)成分中に含まれる水酸基のモル濃度を計算して求めた。具体的には、第一組成物(1)中では、(B)成分のフェニルグリシジルエーテルアクリレートが水酸基を有しており、その水酸基の濃度は、0.0045mol/gである。(A)、(B)、(C)成分を前記配合量で混合し、(A)、(B)、(C)成分中に含まれる水酸基の濃度として計算すると、471×10-6mol/gとなる。
また、ウレタン結合の濃度は、(A)、(B)、(C)成分中に含まれるウレタン結合のモル濃度を計算して求めた。具体的には、第一組成物(1)中には、(A)成分のUA-1、UA-5、およびUA-6がウレタン結合を含有しており、それぞれモル濃度は、19×10-6mol/g、44×10-6mol/g、22×10-6mol/gである。(A)、(B)、(C)成分を前記配合量で混合し、(A)、(B)、(C)成分中に含まれるウレタン結合の濃度として計算すると、85×10-6mol/gとなる。 (First composition)
First composition (1):
(A) 20 parts by weight of UA-1, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by mass of the ester M-600A) were uniformly mixed, and then 100 parts by mass of the mixture was mixed with bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF) as the component (D) , IRGACURE (registered trademark) 819), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and antioxidant (manufactured by BASF) , PUR 68) is uniformly dissolved and mixed, and then 100 parts by mass of the mixture is mixed with terminally methylated polypropylene glycol as component (C). Lumpur (number average molecular weight calculated from the hydroxyl value: 1200) homogeneously dissolved 42.9 parts by weight of the mixed, to obtain a first composition (1).
The viscosity at 25 ° C. of the first composition (1) was 3.2 Pa · s. The concentration of the hydroxyl group in the first composition (1) is 471 × 10 −6 mol / g, the concentration of the urethane bond is 85 × 10 −6 mol / g, and the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 556 × 10 −6 mol / g, and the SP value was 18.2 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react during curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
In addition, the method of calculating | requiring the density | concentration of a hydroxyl group calculated | required by calculating the molar concentration of the hydroxyl group contained in (A), (B), (C) component. Specifically, in the first composition (1), the phenyl glycidyl ether acrylate of the component (B) has a hydroxyl group, and the concentration of the hydroxyl group is 0.0045 mol / g. When the components (A), (B), and (C) are mixed in the above blending amounts and calculated as the concentration of the hydroxyl group contained in the components (A), (B), and (C), 471 × 10 −6 mol / g.
The urethane bond concentration was determined by calculating the molar concentration of the urethane bond contained in the components (A), (B), and (C). Specifically, in the first composition (1), the components (A) UA-1, UA-5, and UA-6 contain a urethane bond, and the molar concentration thereof is 19 × 10 −6 mol / g, 44 × 10 −6 mol / g, and 22 × 10 −6 mol / g. When the components (A), (B), and (C) are mixed in the above amounts and calculated as the concentration of urethane bonds contained in the components (A), (B), and (C), 85 × 10 −6 mol / G.
第一組成物(1):
(A)成分としてUA-1の20質量部、UA-5の32.5質量部、およびUA-6の32.5質量部、(B)成分としてフェニルグリシジルエーテルアクリレート(共栄社化学社製、エポキシエステル M-600A)の15質量部を均一に混合し、その後、該混合物の100質量部に、(D)成分としてビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させて混合し、その後、該混合物の100質量部に(C)成分として末端メチル化したポリプロピレングリコール(水酸基価より算出した数平均分子量:1200)の42.9質量部を均一に溶解させて混合し、第一組成物(1)を得た。
第一組成物(1)の25℃における粘度は、3.2Pa・sであった。第一組成物(1)中の水酸基の濃度は、471×10-6mol/g、ウレタン結合の濃度は、85×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、556×10-6mol/g、SP値は、18.2(J/cm3)1/2であった。水酸基、およびウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。
なお、水酸基の濃度の求め方は、(A)、(B)、(C)成分中に含まれる水酸基のモル濃度を計算して求めた。具体的には、第一組成物(1)中では、(B)成分のフェニルグリシジルエーテルアクリレートが水酸基を有しており、その水酸基の濃度は、0.0045mol/gである。(A)、(B)、(C)成分を前記配合量で混合し、(A)、(B)、(C)成分中に含まれる水酸基の濃度として計算すると、471×10-6mol/gとなる。
また、ウレタン結合の濃度は、(A)、(B)、(C)成分中に含まれるウレタン結合のモル濃度を計算して求めた。具体的には、第一組成物(1)中には、(A)成分のUA-1、UA-5、およびUA-6がウレタン結合を含有しており、それぞれモル濃度は、19×10-6mol/g、44×10-6mol/g、22×10-6mol/gである。(A)、(B)、(C)成分を前記配合量で混合し、(A)、(B)、(C)成分中に含まれるウレタン結合の濃度として計算すると、85×10-6mol/gとなる。 (First composition)
First composition (1):
(A) 20 parts by weight of UA-1, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by mass of the ester M-600A) were uniformly mixed, and then 100 parts by mass of the mixture was mixed with bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF) as the component (D) , IRGACURE (registered trademark) 819), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and antioxidant (manufactured by BASF) , PUR 68) is uniformly dissolved and mixed, and then 100 parts by mass of the mixture is mixed with terminally methylated polypropylene glycol as component (C). Lumpur (number average molecular weight calculated from the hydroxyl value: 1200) homogeneously dissolved 42.9 parts by weight of the mixed, to obtain a first composition (1).
The viscosity at 25 ° C. of the first composition (1) was 3.2 Pa · s. The concentration of the hydroxyl group in the first composition (1) is 471 × 10 −6 mol / g, the concentration of the urethane bond is 85 × 10 −6 mol / g, and the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 556 × 10 −6 mol / g, and the SP value was 18.2 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react during curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
In addition, the method of calculating | requiring the density | concentration of a hydroxyl group calculated | required by calculating the molar concentration of the hydroxyl group contained in (A), (B), (C) component. Specifically, in the first composition (1), the phenyl glycidyl ether acrylate of the component (B) has a hydroxyl group, and the concentration of the hydroxyl group is 0.0045 mol / g. When the components (A), (B), and (C) are mixed in the above blending amounts and calculated as the concentration of the hydroxyl group contained in the components (A), (B), and (C), 471 × 10 −6 mol / g.
The urethane bond concentration was determined by calculating the molar concentration of the urethane bond contained in the components (A), (B), and (C). Specifically, in the first composition (1), the components (A) UA-1, UA-5, and UA-6 contain a urethane bond, and the molar concentration thereof is 19 × 10 −6 mol / g, 44 × 10 −6 mol / g, and 22 × 10 −6 mol / g. When the components (A), (B), and (C) are mixed in the above amounts and calculated as the concentration of urethane bonds contained in the components (A), (B), and (C), 85 × 10 −6 mol / G.
第一組成物(2):
(A)成分としてUA-2の20質量部、UA-5の32.5質量部、およびUA-6の32.5質量部、(B)成分としてフェニルグリシジルエーテルアクリレート(共栄社化学社製、エポキシエステル M-600A)の15質量部を均一に混合し、その後、該混合物の100質量部に、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させて混合し、その後、該混合物の100質量部に(C)成分として末端メチル化したポリプロピレングリコール(水酸基価より算出した数平均分子量:1200)の66.7質量部を均一に溶解させて混合し、第一組成物(2)を得た。
第一組成物(2)の25℃における粘度は、1.5Pa・sであった。第一組成物(2)中の水酸基の濃度は、398×10-6mol/g、ウレタン結合の濃度は、85×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、483×10-6mol/g、SP値は、18.2(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (2):
(A) 20 parts by weight of UA-2, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by weight of the ester M-600A) were uniformly mixed, and then 3 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184) was added to 100 parts by weight of the mixture. , 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 part by mass of an antioxidant (manufactured by BASF, PUR 68) After mixing, 100 parts by mass of the mixture was terminal methylated as component (C) polypropylene glycol (number average molecular weight calculated from hydroxyl value: 1 00) was uniformly dissolved 66.7 parts by weight of the mixed, to obtain a first composition (2).
The viscosity at 25 ° C. of the first composition (2) was 1.5 Pa · s. The concentration of hydroxyl groups in the first composition (2) is 398 × 10 −6 mol / g, the concentration of urethane bonds is 85 × 10 −6 mol / g, and the total of the concentration of hydroxyl groups and the concentration of urethane bonds is 483 × 10 −6 mol / g, and the SP value was 18.2 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
(A)成分としてUA-2の20質量部、UA-5の32.5質量部、およびUA-6の32.5質量部、(B)成分としてフェニルグリシジルエーテルアクリレート(共栄社化学社製、エポキシエステル M-600A)の15質量部を均一に混合し、その後、該混合物の100質量部に、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させて混合し、その後、該混合物の100質量部に(C)成分として末端メチル化したポリプロピレングリコール(水酸基価より算出した数平均分子量:1200)の66.7質量部を均一に溶解させて混合し、第一組成物(2)を得た。
第一組成物(2)の25℃における粘度は、1.5Pa・sであった。第一組成物(2)中の水酸基の濃度は、398×10-6mol/g、ウレタン結合の濃度は、85×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、483×10-6mol/g、SP値は、18.2(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (2):
(A) 20 parts by weight of UA-2, 32.5 parts by weight of UA-5, and 32.5 parts by weight of UA-6 as component (A) Phenyl glycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., epoxy) 15 parts by weight of the ester M-600A) were uniformly mixed, and then 3 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184) was added to 100 parts by weight of the mixture. , 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 part by mass of an antioxidant (manufactured by BASF, PUR 68) After mixing, 100 parts by mass of the mixture was terminal methylated as component (C) polypropylene glycol (number average molecular weight calculated from hydroxyl value: 1 00) was uniformly dissolved 66.7 parts by weight of the mixed, to obtain a first composition (2).
The viscosity at 25 ° C. of the first composition (2) was 1.5 Pa · s. The concentration of hydroxyl groups in the first composition (2) is 398 × 10 −6 mol / g, the concentration of urethane bonds is 85 × 10 −6 mol / g, and the total of the concentration of hydroxyl groups and the concentration of urethane bonds is 483 × 10 −6 mol / g, and the SP value was 18.2 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
第一組成物(3):
(A)成分としてポリイソプレンメタクリレート(クラレ社製、UC203)の25.7質量部、(B)成分としてジシクロペンテニルオキシエチルメタクリレートの7.7質量部、2-ヒドロキシプロピルアクリレートの2.6質量部、(C)成分としてポリブタジエン(エボニックデグサ社製、Polyoil 110)の54.1質量部、(D)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の1.8質量部、および2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(LAMBSON社製、スピードキュアTPO)の0.4質量部を均一に混合し第一組成物(3)を得た。
第一組成物(3)の25℃における粘度は、2.5Pa・sであった。第一組成物(3)中の水酸基の濃度は、220×10-6mol/g、ウレタン結合の濃度は、0mol/g、水酸基の濃度とウレタン結合の濃度との合計は、220×10-6mol/g、SP値は、18.0(J/cm3)1/2であった。水酸基は、硬化時に反応しないため、硬化後の水酸基の濃度も変化しない。 First composition (3):
(A) 25.7 parts by mass of polyisoprene methacrylate (manufactured by Kuraray Co., Ltd., UC203) as component (A), 7.7 parts by mass of dicyclopentenyloxyethyl methacrylate as component (B), 2.6 masses of 2-hydroxypropyl acrylate Part, (C) component 54.1 parts by weight of polybutadiene (Evonik Degussa, Polyoil 110), (D) component 1-hydroxy-cyclohexyl-phenyl-ketone (BASF, IRGACURE (registered trademark) 184) And 0.4 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by LAMBSON, Speed Cure TPO) were uniformly mixed to obtain a first composition (3). .
The viscosity at 25 ° C. of the first composition (3) was 2.5 Pa · s. The concentration of the hydroxyl group in the first composition (3) is 220 × 10 −6 mol / g, the concentration of the urethane bond is 0 mol / g, and the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 220 × 10 − 6 mol / g, SP value, 18.0 (J / cm 3) was 1/2. Since the hydroxyl group does not react during curing, the concentration of the hydroxyl group after curing does not change.
(A)成分としてポリイソプレンメタクリレート(クラレ社製、UC203)の25.7質量部、(B)成分としてジシクロペンテニルオキシエチルメタクリレートの7.7質量部、2-ヒドロキシプロピルアクリレートの2.6質量部、(C)成分としてポリブタジエン(エボニックデグサ社製、Polyoil 110)の54.1質量部、(D)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の1.8質量部、および2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド(LAMBSON社製、スピードキュアTPO)の0.4質量部を均一に混合し第一組成物(3)を得た。
第一組成物(3)の25℃における粘度は、2.5Pa・sであった。第一組成物(3)中の水酸基の濃度は、220×10-6mol/g、ウレタン結合の濃度は、0mol/g、水酸基の濃度とウレタン結合の濃度との合計は、220×10-6mol/g、SP値は、18.0(J/cm3)1/2であった。水酸基は、硬化時に反応しないため、硬化後の水酸基の濃度も変化しない。 First composition (3):
(A) 25.7 parts by mass of polyisoprene methacrylate (manufactured by Kuraray Co., Ltd., UC203) as component (A), 7.7 parts by mass of dicyclopentenyloxyethyl methacrylate as component (B), 2.6 masses of 2-hydroxypropyl acrylate Part, (C) component 54.1 parts by weight of polybutadiene (Evonik Degussa, Polyoil 110), (D) component 1-hydroxy-cyclohexyl-phenyl-ketone (BASF, IRGACURE (registered trademark) 184) And 0.4 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by LAMBSON, Speed Cure TPO) were uniformly mixed to obtain a first composition (3). .
The viscosity at 25 ° C. of the first composition (3) was 2.5 Pa · s. The concentration of the hydroxyl group in the first composition (3) is 220 × 10 −6 mol / g, the concentration of the urethane bond is 0 mol / g, and the sum of the concentration of the hydroxyl group and the concentration of the urethane bond is 220 × 10 − 6 mol / g, SP value, 18.0 (J / cm 3) was 1/2. Since the hydroxyl group does not react during curing, the concentration of the hydroxyl group after curing does not change.
第一組成物(4):
(A)成分としてUA-3の40質量部、(B)成分として2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステル HOB)の40質量部、n-ドデシルメタクリレートの20質量部を均一に混合し、該混合物の100質量部に、(D)成分としてビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.5質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、IRGANOX(登録商標)1010)の0.3質量部を均一に溶解させた。その後、該混合物の100質量部に、(C)成分として非硬化性オリゴマー(1)の42.9質量部を均一に溶解、混合し第一組成物(4)を得た。
第一組成物(4)の25℃における粘度は、3.0Pa・sであった。第一組成物(4)中の水酸基の濃度は、1925×10-6mol/g、ウレタン結合の濃度は、161×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、2086×10-6mol/g、SP値は、20.3(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (4):
40 parts by mass of UA-3 as component (A), 40 parts by mass of 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd., light ester HOB) as component (B), and 20 parts by mass of n-dodecyl methacrylate are uniformly mixed. In addition, to 100 parts by mass of the mixture, 0.5 part by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE (registered trademark) 819) as component (D), 0.04 part by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.3 part by mass of an antioxidant (manufactured by BASF, IRGANOX (registered trademark) 1010) It was dissolved uniformly. Thereafter, 42.9 parts by mass of the non-curable oligomer (1) as the component (C) were uniformly dissolved and mixed in 100 parts by mass of the mixture to obtain a first composition (4).
The viscosity at 25 ° C. of the first composition (4) was 3.0 Pa · s. The concentration of hydroxyl groups in the first composition (4) is 1925 × 10 −6 mol / g, the concentration of urethane bonds is 161 × 10 −6 mol / g, and the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is , 2086 × 10 -6 mol / g , SP value, 20.3 (J / cm 3) was 1/2. Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
(A)成分としてUA-3の40質量部、(B)成分として2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステル HOB)の40質量部、n-ドデシルメタクリレートの20質量部を均一に混合し、該混合物の100質量部に、(D)成分としてビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.5質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、IRGANOX(登録商標)1010)の0.3質量部を均一に溶解させた。その後、該混合物の100質量部に、(C)成分として非硬化性オリゴマー(1)の42.9質量部を均一に溶解、混合し第一組成物(4)を得た。
第一組成物(4)の25℃における粘度は、3.0Pa・sであった。第一組成物(4)中の水酸基の濃度は、1925×10-6mol/g、ウレタン結合の濃度は、161×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、2086×10-6mol/g、SP値は、20.3(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (4):
40 parts by mass of UA-3 as component (A), 40 parts by mass of 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd., light ester HOB) as component (B), and 20 parts by mass of n-dodecyl methacrylate are uniformly mixed. In addition, to 100 parts by mass of the mixture, 0.5 part by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE (registered trademark) 819) as component (D), 0.04 part by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.3 part by mass of an antioxidant (manufactured by BASF, IRGANOX (registered trademark) 1010) It was dissolved uniformly. Thereafter, 42.9 parts by mass of the non-curable oligomer (1) as the component (C) were uniformly dissolved and mixed in 100 parts by mass of the mixture to obtain a first composition (4).
The viscosity at 25 ° C. of the first composition (4) was 3.0 Pa · s. The concentration of hydroxyl groups in the first composition (4) is 1925 × 10 −6 mol / g, the concentration of urethane bonds is 161 × 10 −6 mol / g, and the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is , 2086 × 10 -6 mol / g , SP value, 20.3 (J / cm 3) was 1/2. Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
第一組成物(5):
(A)成分としてUA-4の50質量部、(B)成分として4-ヒドロキシブチルアクリレートの50質量部を均一に混合し、該混合物の100質量部に、(D)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させた。その後、該混合物の100質量部に、(C)成分として非硬化性オリゴマー(1)の150質量部を均一に溶解、混合し第一組成物(5)を得た。
第一組成物(5)の25℃における粘度は、5.9Pa・sであった。第一組成物(5)中の水酸基の濃度は、1850×10-6mol/g、ウレタン結合の濃度は、74×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、1924×10-6mol/g、SP値は、19.6(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (5):
50 parts by mass of UA-4 as component (A) and 50 parts by mass of 4-hydroxybutyl acrylate as component (B) are uniformly mixed, and 100 parts by mass of the mixture is mixed with 1-hydroxy- 3 parts by mass of cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and One part by mass of an antioxidant (manufactured by BASF, PUR 68) was uniformly dissolved. Thereafter, 150 parts by mass of the non-curable oligomer (1) as component (C) was uniformly dissolved and mixed in 100 parts by mass of the mixture to obtain a first composition (5).
The viscosity at 25 ° C. of the first composition (5) was 5.9 Pa · s. The concentration of hydroxyl groups in the first composition (5) is 1850 × 10 −6 mol / g, the concentration of urethane bonds is 74 × 10 −6 mol / g, and the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is 1924 × 10 −6 mol / g, and the SP value was 19.6 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
(A)成分としてUA-4の50質量部、(B)成分として4-ヒドロキシブチルアクリレートの50質量部を均一に混合し、該混合物の100質量部に、(D)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、PUR 68)の1質量部を均一に溶解させた。その後、該混合物の100質量部に、(C)成分として非硬化性オリゴマー(1)の150質量部を均一に溶解、混合し第一組成物(5)を得た。
第一組成物(5)の25℃における粘度は、5.9Pa・sであった。第一組成物(5)中の水酸基の濃度は、1850×10-6mol/g、ウレタン結合の濃度は、74×10-6mol/g、水酸基の濃度とウレタン結合の濃度との合計は、1924×10-6mol/g、SP値は、19.6(J/cm3)1/2であった。水酸基、ウレタン結合は、硬化時に反応しないため、硬化後の水酸基の濃度、ウレタン結合の濃度も変化しない。 First composition (5):
50 parts by mass of UA-4 as component (A) and 50 parts by mass of 4-hydroxybutyl acrylate as component (B) are uniformly mixed, and 100 parts by mass of the mixture is mixed with 1-hydroxy- 3 parts by mass of cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE® 184), 0.04 parts by mass of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), and One part by mass of an antioxidant (manufactured by BASF, PUR 68) was uniformly dissolved. Thereafter, 150 parts by mass of the non-curable oligomer (1) as component (C) was uniformly dissolved and mixed in 100 parts by mass of the mixture to obtain a first composition (5).
The viscosity at 25 ° C. of the first composition (5) was 5.9 Pa · s. The concentration of hydroxyl groups in the first composition (5) is 1850 × 10 −6 mol / g, the concentration of urethane bonds is 74 × 10 −6 mol / g, and the sum of the concentration of hydroxyl groups and the concentration of urethane bonds is 1924 × 10 −6 mol / g, and the SP value was 19.6 (J / cm 3 ) 1/2 . Since the hydroxyl group and the urethane bond do not react at the time of curing, the concentration of the hydroxyl group after curing and the concentration of the urethane bond do not change.
(第二組成物)
第二組成物(1):
(F)成分としてUA-4の55質量部、(G)成分として4-ヒドロキシブチルアクリレート(大阪有機化学工業社製、4HBA)の45質量部を均一に混合して混合物を得た。該混合物の100質量部に、(E)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3.0質量部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.5質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、IRGANOX(登録商標)1010)の0.3質量部を均一に混合し、ベース組成物を得た。ベース組成物の75質量部に、非硬化性オリゴマー(1)の25質量部を均一に溶解させ、第二組成物(1)を得た。第二組成物(1)の25℃における粘度は、60Pa・sであった。 (Second composition)
Second composition (1):
As a component (F), 55 parts by mass of UA-4 and as a component (G) 45 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4HBA) were uniformly mixed to obtain a mixture. To 100 parts by mass of the mixture, 3.0 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE (registered trademark) 184) as component (E), bis (2,4,6-trimethyl) 0.5 part by mass of benzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE® 819), 0.04 of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) A base composition was obtained by uniformly mixing 0.3 parts by mass of an antioxidant and an antioxidant (IRGANOX (registered trademark) 1010, manufactured by BASF). 25 parts by mass of the non-curable oligomer (1) was uniformly dissolved in 75 parts by mass of the base composition to obtain a second composition (1). The viscosity at 25 ° C. of the second composition (1) was 60 Pa · s.
第二組成物(1):
(F)成分としてUA-4の55質量部、(G)成分として4-ヒドロキシブチルアクリレート(大阪有機化学工業社製、4HBA)の45質量部を均一に混合して混合物を得た。該混合物の100質量部に、(E)成分として1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(BASF社製、IRGACURE(登録商標)184)の3.0質量部、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(BASF社製、IRGACURE(登録商標)819)の0.5質量部、2,5-ジ-tert-ブチルヒドロキノン(重合禁止剤、東京化成社製)の0.04質量部、および酸化防止剤(BASF社製、IRGANOX(登録商標)1010)の0.3質量部を均一に混合し、ベース組成物を得た。ベース組成物の75質量部に、非硬化性オリゴマー(1)の25質量部を均一に溶解させ、第二組成物(1)を得た。第二組成物(1)の25℃における粘度は、60Pa・sであった。 (Second composition)
Second composition (1):
As a component (F), 55 parts by mass of UA-4 and as a component (G) 45 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4HBA) were uniformly mixed to obtain a mixture. To 100 parts by mass of the mixture, 3.0 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, IRGACURE (registered trademark) 184) as component (E), bis (2,4,6-trimethyl) 0.5 part by mass of benzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE® 819), 0.04 of 2,5-di-tert-butylhydroquinone (polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.) A base composition was obtained by uniformly mixing 0.3 parts by mass of an antioxidant and an antioxidant (IRGANOX (registered trademark) 1010, manufactured by BASF). 25 parts by mass of the non-curable oligomer (1) was uniformly dissolved in 75 parts by mass of the base composition to obtain a second composition (1). The viscosity at 25 ° C. of the second composition (1) was 60 Pa · s.
(例1)
粘着層付き透明面材(1)の作製:
一定速度で移動する透明面材(1)の表面に、ダイコータを用いて、第一組成物(1)を400μmの厚さで均一に塗布し、ダイコータの下流側に配置されたLED光源から紫外線を照射し、部分硬化物の層を形成した。
部分硬化物の層の表面に、透明面材(1)より大きい保護フィルム(三井化学東セロ社製、ピュアテクト(登録商標)VLH-9)をラミネートした。
保護フィルム側に配置した高圧水銀光源(USHIO電機社製、UVC-05016S1TA01、照射強度:100mW/cm2)から紫外線を照射し、部分硬化物の層を完全硬化させ、保護フィルムによって保護された粘着層付き透明面材(1)を得た。
照射強度は、照度計(ウシオ電機社製、紫外線強度計ユニメーターUIT-101)を用いて測定した。
例1においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、700Paとなり、粘着層の35℃における貯蔵せん断弾性率は、5300Paとなる。 (Example 1)
Production of transparent face material (1) with adhesive layer:
Using a die coater, the first composition (1) is uniformly applied to the surface of the transparent surface material (1) moving at a constant speed with a thickness of 400 μm, and UV light is emitted from an LED light source disposed downstream of the die coater. Was irradiated to form a partially cured product layer.
A protective film larger than the transparent face material (1) (Puretect (registered trademark) VLH-9, manufactured by Mitsui Chemicals, Inc.) was laminated on the surface of the partially cured product layer.
Adhesion protected by a protective film by irradiating ultraviolet rays from a high-pressure mercury light source (USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 100 mW / cm 2 ) placed on the protective film side to completely cure the partially cured product layer A transparent face material (1) with a layer was obtained.
The irradiation intensity was measured using an illuminance meter (Ushio Electric Co., Ltd., UV intensity meter Unimeter UIT-101).
In Example 1, the storage shear modulus at 35 ° C. of the partially cured product layer is 700 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 5300 Pa.
粘着層付き透明面材(1)の作製:
一定速度で移動する透明面材(1)の表面に、ダイコータを用いて、第一組成物(1)を400μmの厚さで均一に塗布し、ダイコータの下流側に配置されたLED光源から紫外線を照射し、部分硬化物の層を形成した。
部分硬化物の層の表面に、透明面材(1)より大きい保護フィルム(三井化学東セロ社製、ピュアテクト(登録商標)VLH-9)をラミネートした。
保護フィルム側に配置した高圧水銀光源(USHIO電機社製、UVC-05016S1TA01、照射強度:100mW/cm2)から紫外線を照射し、部分硬化物の層を完全硬化させ、保護フィルムによって保護された粘着層付き透明面材(1)を得た。
照射強度は、照度計(ウシオ電機社製、紫外線強度計ユニメーターUIT-101)を用いて測定した。
例1においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、700Paとなり、粘着層の35℃における貯蔵せん断弾性率は、5300Paとなる。 (Example 1)
Production of transparent face material (1) with adhesive layer:
Using a die coater, the first composition (1) is uniformly applied to the surface of the transparent surface material (1) moving at a constant speed with a thickness of 400 μm, and UV light is emitted from an LED light source disposed downstream of the die coater. Was irradiated to form a partially cured product layer.
A protective film larger than the transparent face material (1) (Puretect (registered trademark) VLH-9, manufactured by Mitsui Chemicals, Inc.) was laminated on the surface of the partially cured product layer.
Adhesion protected by a protective film by irradiating ultraviolet rays from a high-pressure mercury light source (USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 100 mW / cm 2 ) placed on the protective film side to completely cure the partially cured product layer A transparent face material (1) with a layer was obtained.
The irradiation intensity was measured using an illuminance meter (Ushio Electric Co., Ltd., UV intensity meter Unimeter UIT-101).
In Example 1, the storage shear modulus at 35 ° C. of the partially cured product layer is 700 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 5300 Pa.
(例2)
粘着層付き透明面材(2)の作製:
第一組成物(1)の代わりに第一組成物(2)を用いた以外は、例1と同様にして保護フィルムによって保護された粘着層付き透明面材(2)を得た。
例2においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、60Paとなり、粘着層の35℃における貯蔵せん断弾性率は、3000Paとなる。 (Example 2)
Production of transparent face material (2) with adhesive layer:
Except having used the 1st composition (2) instead of the 1st composition (1), it carried out similarly to Example 1, and obtained the transparent surface material (2) with the adhesion layer protected by the protective film.
In Example 2, the storage shear modulus at 35 ° C. of the partially cured product layer is 60 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 3000 Pa.
粘着層付き透明面材(2)の作製:
第一組成物(1)の代わりに第一組成物(2)を用いた以外は、例1と同様にして保護フィルムによって保護された粘着層付き透明面材(2)を得た。
例2においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、60Paとなり、粘着層の35℃における貯蔵せん断弾性率は、3000Paとなる。 (Example 2)
Production of transparent face material (2) with adhesive layer:
Except having used the 1st composition (2) instead of the 1st composition (1), it carried out similarly to Example 1, and obtained the transparent surface material (2) with the adhesion layer protected by the protective film.
In Example 2, the storage shear modulus at 35 ° C. of the partially cured product layer is 60 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 3000 Pa.
(例3)
粘着層付き透明面材(3)の作製:
第一組成物(1)の代わりに第一組成物(5)を用いた以外は、例1と同様にして保護フィルムによって保護された粘着層付き透明面材(3)を得た。
例3においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、900Paとなり、粘着層の35℃における貯蔵せん断弾性率は、4600Paとなる。 (Example 3)
Production of transparent face material with adhesive layer (3):
A transparent surface material with an adhesive layer (3) protected by a protective film was obtained in the same manner as in Example 1 except that the first composition (5) was used instead of the first composition (1).
In Example 3, the storage shear modulus at 35 ° C. of the partially cured product layer is 900 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 4600 Pa.
粘着層付き透明面材(3)の作製:
第一組成物(1)の代わりに第一組成物(5)を用いた以外は、例1と同様にして保護フィルムによって保護された粘着層付き透明面材(3)を得た。
例3においては、部分硬化物の層の35℃における貯蔵せん断弾性率は、900Paとなり、粘着層の35℃における貯蔵せん断弾性率は、4600Paとなる。 (Example 3)
Production of transparent face material with adhesive layer (3):
A transparent surface material with an adhesive layer (3) protected by a protective film was obtained in the same manner as in Example 1 except that the first composition (5) was used instead of the first composition (1).
In Example 3, the storage shear modulus at 35 ° C. of the partially cured product layer is 900 Pa, and the storage shear modulus at 35 ° C. of the adhesive layer is 4600 Pa.
(泡消え性試験1)
常圧下にて、粘着層付き透明面材(1)から保護フィルムを剥離した。粘着層付き透明面材(1)を、一対の定盤の昇降装置が設置されている減圧装置内の上定盤に、粘着層の面が下向きになるように、粘着パッドと静電チャックを用いて保持した。
被貼合物(1)を、減圧装置内の昇降装置の下定盤の上に、被貼合物(1)に貼合された偏光板が粘着層付き透明面材(1)の粘着層と対向し、粘着層付き透明面材(1)と偏光板の中心箇所が一致するように配置して、粘着層付き透明面材(1)との距離が30mmとなるように保持した。
減圧装置を密封状態として減圧装置内の圧力が約100Paとなるまで排気し、10分間保持した。ついで一旦常圧に戻し1分間保持した。ついで減圧装置内の圧力が約10Paとなるまで排気し、1分間保持した後、減圧装置内の昇降装置にて上下の定盤を接近させ、被貼合物(1)に貼合された偏光板と粘着層付き透明面材(1)とを、粘着層を介して2kPaの圧力で圧着し、10秒間保持した。静電チャックを除電して上定盤から被貼合物(1)を離間させ、約20秒で減圧装置内を大気圧に戻し、模擬表示装置を得た。
模擬表示装置を、粘着層付き透明面材(1)との積層直後に観察したところ、被貼合物(1)に貼合された偏光板と粘着層付き透明面材(1)の粘着層との界面に微細な気泡が多数見られた。模擬表示装置を放置し、気泡が消滅するまでの時間(泡消え時間)を測定した。結果を表1に例1として示す。泡消え時間は、3つのサンプルの結果の平均とした。 (Bubble disappearance test 1)
The protective film was peeled off from the transparent surface material (1) with an adhesive layer under normal pressure. Place the adhesive pad and electrostatic chuck on the upper surface plate in the decompression device where the lifting device for the pair of surface plates is installed so that the surface of the adhesive layer faces downward. Used and held.
The polarizing plate bonded to the object to be bonded (1) on the lower surface plate of the lifting device in the decompression device with the object to be bonded (1) and the adhesive layer of the transparent surface material with an adhesive layer (1) Opposing, arrange | positioning so that the center location of a transparent surface material (1) with an adhesion layer and a polarizing plate may correspond, and it hold | maintained so that the distance with a transparent surface material (1) with an adhesion layer might be set to 30 mm.
The decompression device was sealed and evacuated until the pressure in the decompression device reached about 100 Pa, and held for 10 minutes. Next, the pressure was returned to normal pressure and held for 1 minute. Next, after exhausting until the pressure in the decompression device reaches about 10 Pa and holding for 1 minute, the upper and lower surface plates are brought close to each other by the lifting device in the decompression device, and the polarized light pasted on the object to be bonded (1). The plate and the transparent face material (1) with the adhesive layer were pressure-bonded with a pressure of 2 kPa through the adhesive layer and held for 10 seconds. The electrostatic chuck was neutralized and the object to be bonded (1) was separated from the upper surface plate, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a simulated display device.
When the simulated display device was observed immediately after being laminated with the transparent surface material with adhesive layer (1), the polarizing plate bonded to the object to be bonded (1) and the adhesive layer of the transparent surface material with adhesive layer (1) Many fine bubbles were seen at the interface. The simulated display device was allowed to stand, and the time until bubbles disappeared (bubble disappearance time) was measured. The results are shown in Table 1 as Example 1. The bubble disappearance time was the average of the results of three samples.
常圧下にて、粘着層付き透明面材(1)から保護フィルムを剥離した。粘着層付き透明面材(1)を、一対の定盤の昇降装置が設置されている減圧装置内の上定盤に、粘着層の面が下向きになるように、粘着パッドと静電チャックを用いて保持した。
被貼合物(1)を、減圧装置内の昇降装置の下定盤の上に、被貼合物(1)に貼合された偏光板が粘着層付き透明面材(1)の粘着層と対向し、粘着層付き透明面材(1)と偏光板の中心箇所が一致するように配置して、粘着層付き透明面材(1)との距離が30mmとなるように保持した。
減圧装置を密封状態として減圧装置内の圧力が約100Paとなるまで排気し、10分間保持した。ついで一旦常圧に戻し1分間保持した。ついで減圧装置内の圧力が約10Paとなるまで排気し、1分間保持した後、減圧装置内の昇降装置にて上下の定盤を接近させ、被貼合物(1)に貼合された偏光板と粘着層付き透明面材(1)とを、粘着層を介して2kPaの圧力で圧着し、10秒間保持した。静電チャックを除電して上定盤から被貼合物(1)を離間させ、約20秒で減圧装置内を大気圧に戻し、模擬表示装置を得た。
模擬表示装置を、粘着層付き透明面材(1)との積層直後に観察したところ、被貼合物(1)に貼合された偏光板と粘着層付き透明面材(1)の粘着層との界面に微細な気泡が多数見られた。模擬表示装置を放置し、気泡が消滅するまでの時間(泡消え時間)を測定した。結果を表1に例1として示す。泡消え時間は、3つのサンプルの結果の平均とした。 (Bubble disappearance test 1)
The protective film was peeled off from the transparent surface material (1) with an adhesive layer under normal pressure. Place the adhesive pad and electrostatic chuck on the upper surface plate in the decompression device where the lifting device for the pair of surface plates is installed so that the surface of the adhesive layer faces downward. Used and held.
The polarizing plate bonded to the object to be bonded (1) on the lower surface plate of the lifting device in the decompression device with the object to be bonded (1) and the adhesive layer of the transparent surface material with an adhesive layer (1) Opposing, arrange | positioning so that the center location of a transparent surface material (1) with an adhesion layer and a polarizing plate may correspond, and it hold | maintained so that the distance with a transparent surface material (1) with an adhesion layer might be set to 30 mm.
The decompression device was sealed and evacuated until the pressure in the decompression device reached about 100 Pa, and held for 10 minutes. Next, the pressure was returned to normal pressure and held for 1 minute. Next, after exhausting until the pressure in the decompression device reaches about 10 Pa and holding for 1 minute, the upper and lower surface plates are brought close to each other by the lifting device in the decompression device, and the polarized light pasted on the object to be bonded (1). The plate and the transparent face material (1) with the adhesive layer were pressure-bonded with a pressure of 2 kPa through the adhesive layer and held for 10 seconds. The electrostatic chuck was neutralized and the object to be bonded (1) was separated from the upper surface plate, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a simulated display device.
When the simulated display device was observed immediately after being laminated with the transparent surface material with adhesive layer (1), the polarizing plate bonded to the object to be bonded (1) and the adhesive layer of the transparent surface material with adhesive layer (1) Many fine bubbles were seen at the interface. The simulated display device was allowed to stand, and the time until bubbles disappeared (bubble disappearance time) was measured. The results are shown in Table 1 as Example 1. The bubble disappearance time was the average of the results of three samples.
(泡消え性試験2)
粘着層付き透明面材(1)の代わりに粘着層付き透明面材(2)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表1に例2として示す。 (Bubble extinction test 2)
A simulated display device was produced in the same manner as in thefoam extinction test 1 except that the transparent face material with an adhesive layer (2) was used instead of the transparent face material with an adhesive layer (1), and the foam disappearance time was measured. The results are shown in Table 1 as Example 2.
粘着層付き透明面材(1)の代わりに粘着層付き透明面材(2)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表1に例2として示す。 (Bubble extinction test 2)
A simulated display device was produced in the same manner as in the
(泡消え性試験3)
粘着層付き透明面材(1)の代わりに粘着層付き透明面材(3)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表1に例3として示す。 (Bubble extinction test 3)
A simulated display device was produced in the same manner as in thefoam extinction test 1 except that the transparent face material with an adhesive layer (3) was used instead of the transparent face material with an adhesive layer (1), and the bubble disappearance time was measured. The results are shown in Table 1 as Example 3.
粘着層付き透明面材(1)の代わりに粘着層付き透明面材(3)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表1に例3として示す。 (Bubble extinction test 3)
A simulated display device was produced in the same manner as in the
(90度ピール試験)
保護フィルムによって保護された粘着層付き透明面材(1)~(3)の保護フィルムと粘着層に幅25mm、長さ約90mmの切れ込みを入れた。その長辺側の一端を約30mm剥離して粘着力測定器(島津製作所社製、オートグラフ)にセットし、90度ピール試験を行った。それぞれの結果を表1に例1~例3として示す。なお、剥離速度は60mm/分であった。判定基準は、下記のとおりである
○:界面剥離(ガラス側に粘着層が残らない)。
×:凝集破壊(粘着層が剥離途中で切れ、ガラスと保護フィルムの両方に粘着層が残る)。 (90 degree peel test)
The transparent film with adhesive layer protected by the protective film (1) to (3) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm. One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed. The respective results are shown in Table 1 as Examples 1 to 3. The peeling speed was 60 mm / min. The judgment criteria are as follows: ○: Interfacial peeling (no adhesive layer left on the glass side).
X: Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
保護フィルムによって保護された粘着層付き透明面材(1)~(3)の保護フィルムと粘着層に幅25mm、長さ約90mmの切れ込みを入れた。その長辺側の一端を約30mm剥離して粘着力測定器(島津製作所社製、オートグラフ)にセットし、90度ピール試験を行った。それぞれの結果を表1に例1~例3として示す。なお、剥離速度は60mm/分であった。判定基準は、下記のとおりである
○:界面剥離(ガラス側に粘着層が残らない)。
×:凝集破壊(粘着層が剥離途中で切れ、ガラスと保護フィルムの両方に粘着層が残る)。 (90 degree peel test)
The transparent film with adhesive layer protected by the protective film (1) to (3) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm. One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed. The respective results are shown in Table 1 as Examples 1 to 3. The peeling speed was 60 mm / min. The judgment criteria are as follows: ○: Interfacial peeling (no adhesive layer left on the glass side).
X: Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
例1~3における粘着層中の水酸基の濃度と泡消え時間とのグラフを図13に示す。例1~3における粘着層中の水酸基の濃度およびウレタン結合の濃度の合計と泡消え時間とのグラフを図14に示す。粘着層中の水酸基の濃度およびウレタン結合の濃度と、泡消え時間との間に相関関係があることがわかる。
なお、図13における横軸の水酸基の濃度の単位、及び図14における横軸の水酸基の濃度およびウレタン結合の濃度の合計の単位は、モル/(g×106)である。 A graph of the concentration of the hydroxyl group in the adhesive layer and the bubble disappearance time in Examples 1 to 3 is shown in FIG. FIG. 14 shows a graph of the total concentration of the hydroxyl groups and urethane bonds in the adhesive layers in Examples 1 to 3 and the bubble disappearance time. It can be seen that there is a correlation between the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer and the bubble disappearance time.
The unit of hydroxyl group concentration on the horizontal axis in FIG. 13 and the total unit of hydroxyl group concentration and urethane bond concentration on the horizontal axis in FIG. 14 are mol / (g × 10 6 ).
なお、図13における横軸の水酸基の濃度の単位、及び図14における横軸の水酸基の濃度およびウレタン結合の濃度の合計の単位は、モル/(g×106)である。 A graph of the concentration of the hydroxyl group in the adhesive layer and the bubble disappearance time in Examples 1 to 3 is shown in FIG. FIG. 14 shows a graph of the total concentration of the hydroxyl groups and urethane bonds in the adhesive layers in Examples 1 to 3 and the bubble disappearance time. It can be seen that there is a correlation between the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer and the bubble disappearance time.
The unit of hydroxyl group concentration on the horizontal axis in FIG. 13 and the total unit of hydroxyl group concentration and urethane bond concentration on the horizontal axis in FIG. 14 are mol / (g × 10 6 ).
(例4)
粘着層付き透明面材(4)の作製:
透明面材(2)の外周縁から約25mmの位置の全周にわたって、幅約1mm、塗布厚さ約0.6mmとなるように第二組成物(1)をディスペンサにて塗布し、ディスペンサに付随したLED光源から紫外線を照射し、半硬化の堰を形成した。
堰の内側の領域に、第一組成物(1)を、ディスペンサを用いて総質量が2.5gとなるように複数個所に供給した。第一組成物(1)を供給する間、決壊などの破損個所はなく、半硬化の堰の形状は維持されていた。 (Example 4)
Production of transparent face material with adhesive layer (4):
The second composition (1) is applied with a dispenser over the entire circumference at a position of about 25 mm from the outer peripheral edge of the transparent face material (2) so that the width is about 1 mm and the application thickness is about 0.6 mm. A semi-cured weir was formed by irradiating ultraviolet rays from the LED light source attached thereto.
In the region inside the weir, the first composition (1) was supplied to a plurality of locations using a dispenser so that the total mass was 2.5 g. While supplying the first composition (1), there was no breakage such as breakage, and the shape of the semi-cured weir was maintained.
粘着層付き透明面材(4)の作製:
透明面材(2)の外周縁から約25mmの位置の全周にわたって、幅約1mm、塗布厚さ約0.6mmとなるように第二組成物(1)をディスペンサにて塗布し、ディスペンサに付随したLED光源から紫外線を照射し、半硬化の堰を形成した。
堰の内側の領域に、第一組成物(1)を、ディスペンサを用いて総質量が2.5gとなるように複数個所に供給した。第一組成物(1)を供給する間、決壊などの破損個所はなく、半硬化の堰の形状は維持されていた。 (Example 4)
Production of transparent face material with adhesive layer (4):
The second composition (1) is applied with a dispenser over the entire circumference at a position of about 25 mm from the outer peripheral edge of the transparent face material (2) so that the width is about 1 mm and the application thickness is about 0.6 mm. A semi-cured weir was formed by irradiating ultraviolet rays from the LED light source attached thereto.
In the region inside the weir, the first composition (1) was supplied to a plurality of locations using a dispenser so that the total mass was 2.5 g. While supplying the first composition (1), there was no breakage such as breakage, and the shape of the semi-cured weir was maintained.
透明面材(2)を、一対の定盤の昇降装置が設置されている減圧装置内の下定盤の上に、第一組成物(1)が塗布された面が上になるように平置した。保護フィルム付き支持面材を、保護フィルム16が貼合された面を下にして減圧装置内の上定盤に保持した。減圧装置内の圧力が約10000Paとなるまで排気し、その状態で1分間保持した。その後、減圧装置内の昇降装置にて上下の定盤を接近させ、透明面材(2)と、保護フィルム付き支持面材とを、第一組成物(1)を介して2kPaの圧力で圧着し、10秒間保持させて貼合した。貼合後、減圧装置内を大気圧雰囲気に戻し、透明面材(2)、保護フィルムおよび堰で第一組成物(1)からなる未硬化の粘着層を密封した積層体を得た。
The transparent surface material (2) is placed flat on the lower surface plate in the decompression device in which a pair of surface plate lifting devices are installed so that the surface coated with the first composition (1) is on the upper surface. did. The support surface material with the protective film was held on the upper surface plate in the decompression apparatus with the surface on which the protective film 16 was bonded down. It exhausted until the pressure in a decompression device became about 10,000 Pa, and was hold | maintained in that state for 1 minute. Thereafter, the upper and lower surface plates are brought close to each other by a lifting device in the decompression device, and the transparent surface material (2) and the support surface material with the protective film are pressure-bonded through the first composition (1) at a pressure of 2 kPa. And held for 10 seconds for bonding. After pasting, the inside of the decompression device was returned to the atmospheric pressure atmosphere to obtain a laminate in which the uncured adhesive layer made of the first composition (1) was sealed with the transparent surface material (2), the protective film and the weir.
積層体に、支持面材側に配置した高圧水銀光源(照射強度:100mW/cm2)から紫外線を20秒間照射し、半硬化の堰および未硬化の粘着層を硬化させ、粘着層を形成した。硬化後の粘着層の厚さは、0.4mmでほぼ均一であった。
その後、支持面材を剥離することによって、保護フィルムによって保護された粘着層付き透明面材(4)を得た。
例4においては、粘着層の35℃における貯蔵せん断弾性率は、7000Paとなる。 The laminated body was irradiated with ultraviolet rays for 20 seconds from a high-pressure mercury light source (irradiation intensity: 100 mW / cm 2 ) disposed on the support surface material side to cure the semi-cured weir and the uncured adhesive layer to form an adhesive layer. . The thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
Then, the transparent surface material (4) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
In Example 4, the storage shear modulus at 35 ° C. of the adhesive layer is 7000 Pa.
その後、支持面材を剥離することによって、保護フィルムによって保護された粘着層付き透明面材(4)を得た。
例4においては、粘着層の35℃における貯蔵せん断弾性率は、7000Paとなる。 The laminated body was irradiated with ultraviolet rays for 20 seconds from a high-pressure mercury light source (irradiation intensity: 100 mW / cm 2 ) disposed on the support surface material side to cure the semi-cured weir and the uncured adhesive layer to form an adhesive layer. . The thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
Then, the transparent surface material (4) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
In Example 4, the storage shear modulus at 35 ° C. of the adhesive layer is 7000 Pa.
(例5)
粘着層付き透明面材(5)の作製:
第一組成物(1)の代わりに第一組成物(3)を用いた以外は、例4と同様にして保護フィルムによって保護された粘着層付き透明面材(5)を得た。
例5においては、粘着層の35℃における貯蔵せん断弾性率は、10500Paとなる。 (Example 5)
Production of transparent face material with adhesive layer (5):
A transparent surface material (5) with an adhesive layer protected by a protective film was obtained in the same manner as in Example 4 except that the first composition (3) was used instead of the first composition (1).
In Example 5, the storage shear modulus at 35 ° C. of the adhesive layer is 10500 Pa.
粘着層付き透明面材(5)の作製:
第一組成物(1)の代わりに第一組成物(3)を用いた以外は、例4と同様にして保護フィルムによって保護された粘着層付き透明面材(5)を得た。
例5においては、粘着層の35℃における貯蔵せん断弾性率は、10500Paとなる。 (Example 5)
Production of transparent face material with adhesive layer (5):
A transparent surface material (5) with an adhesive layer protected by a protective film was obtained in the same manner as in Example 4 except that the first composition (3) was used instead of the first composition (1).
In Example 5, the storage shear modulus at 35 ° C. of the adhesive layer is 10500 Pa.
(例6)
粘着層付き透明面材(6)の作製:
第一組成物(1)の代わりに第一組成物(4)を用いた以外は、例4と同様にして積層体を得た。
積層体に、支持面材側に配置したケミカルランプ(日本電気社製、FL15BL、照射強度:2mW/cm2)から紫外線を10分間照射し、半硬化の堰および未硬化の粘着層を硬化させ、粘着層を形成した。硬化後の粘着層の厚さは、0.4mmでほぼ均一であった。
その後、支持面材を剥離することによって、保護フィルムによって保護された粘着層付き透明面材(6)を得た。
例6においては、粘着層の35℃における貯蔵せん断弾性率は、181000Paとなる。 (Example 6)
Production of transparent face material (6) with adhesive layer:
A laminate was obtained in the same manner as in Example 4 except that the first composition (4) was used instead of the first composition (1).
The laminated body is irradiated with ultraviolet rays for 10 minutes from a chemical lamp (NEC, FL15BL, irradiation intensity: 2 mW / cm 2 ) disposed on the support surface material side, and the semi-cured weir and the uncured adhesive layer are cured. An adhesive layer was formed. The thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
Then, the transparent surface material (6) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
In Example 6, the storage shear elastic modulus of the adhesive layer at 35 ° C. is 181000 Pa.
粘着層付き透明面材(6)の作製:
第一組成物(1)の代わりに第一組成物(4)を用いた以外は、例4と同様にして積層体を得た。
積層体に、支持面材側に配置したケミカルランプ(日本電気社製、FL15BL、照射強度:2mW/cm2)から紫外線を10分間照射し、半硬化の堰および未硬化の粘着層を硬化させ、粘着層を形成した。硬化後の粘着層の厚さは、0.4mmでほぼ均一であった。
その後、支持面材を剥離することによって、保護フィルムによって保護された粘着層付き透明面材(6)を得た。
例6においては、粘着層の35℃における貯蔵せん断弾性率は、181000Paとなる。 (Example 6)
Production of transparent face material (6) with adhesive layer:
A laminate was obtained in the same manner as in Example 4 except that the first composition (4) was used instead of the first composition (1).
The laminated body is irradiated with ultraviolet rays for 10 minutes from a chemical lamp (NEC, FL15BL, irradiation intensity: 2 mW / cm 2 ) disposed on the support surface material side, and the semi-cured weir and the uncured adhesive layer are cured. An adhesive layer was formed. The thickness of the adhesive layer after curing was approximately uniform at 0.4 mm.
Then, the transparent surface material (6) with the adhesion layer protected by the protective film was obtained by peeling a support surface material.
In Example 6, the storage shear elastic modulus of the adhesive layer at 35 ° C. is 181000 Pa.
(泡消え性試験4)
常圧下にて、粘着層付き透明面材(4)から保護フィルムを剥離した。粘着層付き透明面材(4)を、一対の定盤の昇降装置が設置されている減圧装置内の上定盤に、粘着層の面が下向きになるように、粘着パッドと静電チャックを用いて保持した。
被貼合物(2)を、減圧装置内の昇降装置の下定盤の上に、被貼合物(2)に貼合された偏光板が粘着層付き透明面材(4)の粘着層と対向し、粘着層付き透明面材(4)と偏光板の中心箇所が一致するように配置して、粘着層付き透明面材(4)との距離が30mmとなるように保持させた。
減圧装置を密封状態として減圧装置内の圧力が約10,000Paとなるまで排気し、1分間保持した後、減圧装置内の昇降装置にて上下の定盤を接近させ、被貼合物(2)に貼合された偏光板と粘着層付き透明面材(4)とを、粘着層を介して2kPaの圧力で圧着し、10秒間保持した。静電チャックを除電して上定盤から被貼合物(2)を離間させ、約20秒で減圧装置内を大気圧に戻し、模擬表示装置を得た。
模擬表示装置を、粘着層付き透明面材(4)との積層直後に観察したところ、被貼合物(2)に貼合された偏光板と粘着層付き透明面材(4)の粘着層との界面に微細な気泡が多数見られた。模擬表示装置を放置し、気泡が消滅するまでの時間(泡消え時間)を測定した。結果を表2に例4として示す。泡消え時間は、3つのサンプルの結果の平均とした。 (Foam extinction test 4)
The protective film was peeled off from the transparent surface material (4) with an adhesive layer under normal pressure. The adhesive pad and electrostatic chuck are placed on the upper surface plate in the decompression device where the lifting device for the pair of surface plates is placed so that the surface of the adhesive layer faces downward. Used and held.
The polarizing plate bonded to the object to be bonded (2) on the lower surface plate of the lifting device in the decompression device with the object to be bonded (2) and the adhesive layer of the transparent surface material with an adhesive layer (4) Opposing, arrange | positioning so that the center location of a transparent surface material (4) with an adhesion layer and a polarizing plate may correspond, and it was made to hold | maintain so that the distance with a transparent surface material (4) with an adhesion layer might be set to 30 mm.
Exhaust until the pressure inside the decompression device becomes about 10,000 Pa with the decompression device sealed, and hold for 1 minute, then bring the upper and lower surface plates closer with the lifting device inside the decompression device, and the object to be bonded (2 ) And the pressure-sensitive adhesive layer-attached transparent surface material (4) were pressed with a pressure of 2 kPa through the adhesive layer and held for 10 seconds. The electrostatic chuck was neutralized and the object to be bonded (2) was separated from the upper surface plate, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a simulated display device.
When the simulated display device was observed immediately after lamination with the transparent surface material with the adhesive layer (4), the polarizing plate bonded to the object to be bonded (2) and the adhesive layer of the transparent surface material with the adhesive layer (4) Many fine bubbles were seen at the interface. The simulated display device was allowed to stand, and the time until bubbles disappeared (bubble disappearance time) was measured. The results are shown in Table 2 as Example 4. The bubble disappearance time was the average of the results of three samples.
常圧下にて、粘着層付き透明面材(4)から保護フィルムを剥離した。粘着層付き透明面材(4)を、一対の定盤の昇降装置が設置されている減圧装置内の上定盤に、粘着層の面が下向きになるように、粘着パッドと静電チャックを用いて保持した。
被貼合物(2)を、減圧装置内の昇降装置の下定盤の上に、被貼合物(2)に貼合された偏光板が粘着層付き透明面材(4)の粘着層と対向し、粘着層付き透明面材(4)と偏光板の中心箇所が一致するように配置して、粘着層付き透明面材(4)との距離が30mmとなるように保持させた。
減圧装置を密封状態として減圧装置内の圧力が約10,000Paとなるまで排気し、1分間保持した後、減圧装置内の昇降装置にて上下の定盤を接近させ、被貼合物(2)に貼合された偏光板と粘着層付き透明面材(4)とを、粘着層を介して2kPaの圧力で圧着し、10秒間保持した。静電チャックを除電して上定盤から被貼合物(2)を離間させ、約20秒で減圧装置内を大気圧に戻し、模擬表示装置を得た。
模擬表示装置を、粘着層付き透明面材(4)との積層直後に観察したところ、被貼合物(2)に貼合された偏光板と粘着層付き透明面材(4)の粘着層との界面に微細な気泡が多数見られた。模擬表示装置を放置し、気泡が消滅するまでの時間(泡消え時間)を測定した。結果を表2に例4として示す。泡消え時間は、3つのサンプルの結果の平均とした。 (Foam extinction test 4)
The protective film was peeled off from the transparent surface material (4) with an adhesive layer under normal pressure. The adhesive pad and electrostatic chuck are placed on the upper surface plate in the decompression device where the lifting device for the pair of surface plates is placed so that the surface of the adhesive layer faces downward. Used and held.
The polarizing plate bonded to the object to be bonded (2) on the lower surface plate of the lifting device in the decompression device with the object to be bonded (2) and the adhesive layer of the transparent surface material with an adhesive layer (4) Opposing, arrange | positioning so that the center location of a transparent surface material (4) with an adhesion layer and a polarizing plate may correspond, and it was made to hold | maintain so that the distance with a transparent surface material (4) with an adhesion layer might be set to 30 mm.
Exhaust until the pressure inside the decompression device becomes about 10,000 Pa with the decompression device sealed, and hold for 1 minute, then bring the upper and lower surface plates closer with the lifting device inside the decompression device, and the object to be bonded (2 ) And the pressure-sensitive adhesive layer-attached transparent surface material (4) were pressed with a pressure of 2 kPa through the adhesive layer and held for 10 seconds. The electrostatic chuck was neutralized and the object to be bonded (2) was separated from the upper surface plate, and the inside of the decompression device was returned to atmospheric pressure in about 20 seconds to obtain a simulated display device.
When the simulated display device was observed immediately after lamination with the transparent surface material with the adhesive layer (4), the polarizing plate bonded to the object to be bonded (2) and the adhesive layer of the transparent surface material with the adhesive layer (4) Many fine bubbles were seen at the interface. The simulated display device was allowed to stand, and the time until bubbles disappeared (bubble disappearance time) was measured. The results are shown in Table 2 as Example 4. The bubble disappearance time was the average of the results of three samples.
(泡消え性試験5)
粘着層付き透明面材(4)の代わりに粘着層付き透明面材(5)を用いた以外は、泡消え性試験4と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表2に例5として示す。 (Bubble extinction test 5)
A simulated display device was produced in the same manner as in the foam extinction test 4 except that the transparent face material with an adhesive layer (5) was used instead of the transparent face material with an adhesive layer (4), and the bubble disappearance time was measured. The results are shown in Table 2 as Example 5.
粘着層付き透明面材(4)の代わりに粘着層付き透明面材(5)を用いた以外は、泡消え性試験4と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表2に例5として示す。 (Bubble extinction test 5)
A simulated display device was produced in the same manner as in the foam extinction test 4 except that the transparent face material with an adhesive layer (5) was used instead of the transparent face material with an adhesive layer (4), and the bubble disappearance time was measured. The results are shown in Table 2 as Example 5.
(泡消え性試験6)
粘着層付き透明面材(4)の代わりに粘着層付き透明面材(6)を用いた以外は、泡消え性試験4と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表2に例6として示す。 (Bubble extinction test 6)
A simulated display device was produced in the same manner as in the foam extinction test 4 except that the transparent face material with an adhesive layer (6) was used instead of the transparent face material with an adhesive layer (4), and the foam disappearance time was measured. The results are shown in Table 2 as Example 6.
粘着層付き透明面材(4)の代わりに粘着層付き透明面材(6)を用いた以外は、泡消え性試験4と同様にして模擬表示装置を作製し、泡消え時間を測定した。結果を表2に例6として示す。 (Bubble extinction test 6)
A simulated display device was produced in the same manner as in the foam extinction test 4 except that the transparent face material with an adhesive layer (6) was used instead of the transparent face material with an adhesive layer (4), and the foam disappearance time was measured. The results are shown in Table 2 as Example 6.
(90度ピール試験)
保護フィルムによって保護された粘着層付き透明面材(4)~(6)の保護フィルムと粘着層に幅25mm、長さ約90mmの切れ込みを入れた。その長辺側の一端を約30mm剥離して粘着力測定器(島津製作所社製、オートグラフ)にセットし、90度ピール試験を行った。それぞれの結果を表2に例4~例6として示す。なお、剥離速度は60mm/分であった。判定基準は、下記のとおりである。
○:界面剥離(ガラス側に粘着層が残らない)。
×:凝集破壊(粘着層が剥離途中で切れ、ガラスと保護フィルムの両方に粘着層が残る)。 (90 degree peel test)
The transparent film with adhesive layer protected by the protective film (4) to (6) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm. One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed. The respective results are shown in Table 2 as Examples 4 to 6. The peeling speed was 60 mm / min. Judgment criteria are as follows.
○: Interfacial peeling (no adhesive layer left on the glass side).
X: Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
保護フィルムによって保護された粘着層付き透明面材(4)~(6)の保護フィルムと粘着層に幅25mm、長さ約90mmの切れ込みを入れた。その長辺側の一端を約30mm剥離して粘着力測定器(島津製作所社製、オートグラフ)にセットし、90度ピール試験を行った。それぞれの結果を表2に例4~例6として示す。なお、剥離速度は60mm/分であった。判定基準は、下記のとおりである。
○:界面剥離(ガラス側に粘着層が残らない)。
×:凝集破壊(粘着層が剥離途中で切れ、ガラスと保護フィルムの両方に粘着層が残る)。 (90 degree peel test)
The transparent film with adhesive layer protected by the protective film (4) to (6) was cut into a protective film and adhesive layer having a width of 25 mm and a length of about 90 mm. One end of the long side was peeled off by about 30 mm and set on an adhesive force measuring device (manufactured by Shimadzu Corporation, Autograph), and a 90-degree peel test was performed. The respective results are shown in Table 2 as Examples 4 to 6. The peeling speed was 60 mm / min. Judgment criteria are as follows.
○: Interfacial peeling (no adhesive layer left on the glass side).
X: Cohesive failure (adhesive layer is cut during peeling, and adhesive layer remains on both glass and protective film).
例4~6における粘着層中の水酸基の濃度と泡消え時間とのグラフを図15に示す。例4~6における粘着層中の水酸基の濃度およびウレタン結合の濃度の合計と泡消え時間とのグラフを図16に示す。粘着層中の水酸基の濃度およびウレタン結合の濃度と、泡消え時間との間に相関関係があることがわかる。
FIG. 15 shows a graph of the concentration of the hydroxyl group in the adhesive layer and the bubble disappearance time in Examples 4 to 6. FIG. 16 shows a graph of the total concentration of hydroxyl groups and urethane bonds in the adhesive layers in Examples 4 to 6 and the bubble disappearance time. It can be seen that there is a correlation between the concentration of hydroxyl groups and the concentration of urethane bonds in the adhesive layer and the bubble disappearance time.
(例7)
保護フィルム付き粘着シート(1)の作製:
一定速度で移動する、表面を離型処理したポリエチレンテレフタレート(PET)フィルム(第1基材)(帝人社製 ピューレックス(登録商標))の表面に、ダイコータを用いて、第1組成物(1)を500μmの厚さで連続塗布した後、第1基材よりも表面の離型性の高いPETフィルム(第2基材)(帝人 ピューレックス(登録商標))で挟持した。第1基材側より高圧水銀光源(USHIO電機社製、UVC-05016S1TA01、照射強度:1500mJ/cm2)から紫外線を照射し、第1組成物(1)を完全硬化させ、保護フィルム付き粘着シート(1)を得た。粘着シートの35℃における貯蔵せん断弾性率は5300Paとなる。 (Example 7)
Production of pressure-sensitive adhesive sheet with protective film (1):
Using a die coater on the surface of a polyethylene terephthalate (PET) film (first substrate) (Purex (registered trademark) manufactured by Teijin Ltd.) whose mold has been released, the first composition (1 ) Was continuously applied at a thickness of 500 μm, and then sandwiched with a PET film (second substrate) (Teijin Purex (registered trademark)) having a surface release property higher than that of the first substrate. The first composition (1) is completely cured by irradiating ultraviolet rays from a high-pressure mercury light source (USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 1500 mJ / cm 2 ) from the first base material side, and a pressure-sensitive adhesive sheet with a protective film (1) was obtained. The storage shear modulus of the pressure-sensitive adhesive sheet at 35 ° C. is 5300 Pa.
保護フィルム付き粘着シート(1)の作製:
一定速度で移動する、表面を離型処理したポリエチレンテレフタレート(PET)フィルム(第1基材)(帝人社製 ピューレックス(登録商標))の表面に、ダイコータを用いて、第1組成物(1)を500μmの厚さで連続塗布した後、第1基材よりも表面の離型性の高いPETフィルム(第2基材)(帝人 ピューレックス(登録商標))で挟持した。第1基材側より高圧水銀光源(USHIO電機社製、UVC-05016S1TA01、照射強度:1500mJ/cm2)から紫外線を照射し、第1組成物(1)を完全硬化させ、保護フィルム付き粘着シート(1)を得た。粘着シートの35℃における貯蔵せん断弾性率は5300Paとなる。 (Example 7)
Production of pressure-sensitive adhesive sheet with protective film (1):
Using a die coater on the surface of a polyethylene terephthalate (PET) film (first substrate) (Purex (registered trademark) manufactured by Teijin Ltd.) whose mold has been released, the first composition (1 ) Was continuously applied at a thickness of 500 μm, and then sandwiched with a PET film (second substrate) (Teijin Purex (registered trademark)) having a surface release property higher than that of the first substrate. The first composition (1) is completely cured by irradiating ultraviolet rays from a high-pressure mercury light source (USHIO Electric Co., Ltd., UVC-05016S1TA01, irradiation intensity: 1500 mJ / cm 2 ) from the first base material side, and a pressure-sensitive adhesive sheet with a protective film (1) was obtained. The storage shear modulus of the pressure-sensitive adhesive sheet at 35 ° C. is 5300 Pa.
(泡消え性試験7)
上記保護フィルム付き粘着シートについて、常圧下にて、保護フィルム付き粘着シート(1)の第2基材を剥離して、泡消え性試験に供した。粘着層付き透明面材(1)の代わりに保護フィルム付き粘着シート(1)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作成し、泡消え時間を測定する。泡消え時間は良好である。 (Bubble extinction test 7)
About the said adhesive sheet with a protective film, the 2nd base material of the adhesive sheet with a protective film (1) was peeled off under normal pressure, and it used for the foam extinction test. A simulated display device is prepared in the same manner as in thefoam extinction test 1 except that the adhesive sheet (1) with a protective film is used instead of the transparent surface material (1) with an adhesive layer, and the foam disappearance time is measured. The bubble disappearance time is good.
上記保護フィルム付き粘着シートについて、常圧下にて、保護フィルム付き粘着シート(1)の第2基材を剥離して、泡消え性試験に供した。粘着層付き透明面材(1)の代わりに保護フィルム付き粘着シート(1)を用いた以外は、泡消え性試験1と同様にして模擬表示装置を作成し、泡消え時間を測定する。泡消え時間は良好である。 (Bubble extinction test 7)
About the said adhesive sheet with a protective film, the 2nd base material of the adhesive sheet with a protective film (1) was peeled off under normal pressure, and it used for the foam extinction test. A simulated display device is prepared in the same manner as in the
本発明によれば、被貼合物と透明面材とを粘着層を介して貼合した際に、被貼合物と粘着層との界面に残存する気泡が迅速に消滅し、気泡等の欠点が残存しない粘着層付き透明面材を製造できる。この粘着層付き透明面材は、表示パネルの保護板、座標入力装置の保護板、座標入力装置の透明電極付き基板等として有用である。
なお、2014年4月17日に出願された日本特許出願2014-085423号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。 According to the present invention, when the object to be bonded and the transparent surface material are bonded via the adhesive layer, the bubbles remaining at the interface between the object to be bonded and the adhesive layer quickly disappear, A transparent surface material with an adhesive layer in which no defects remain can be produced. This transparent surface material with an adhesive layer is useful as a protective plate for display panels, a protective plate for coordinate input devices, a substrate with transparent electrodes for coordinate input devices, and the like.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2014-085423 filed on April 17, 2014 are incorporated herein by reference. .
なお、2014年4月17日に出願された日本特許出願2014-085423号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。 According to the present invention, when the object to be bonded and the transparent surface material are bonded via the adhesive layer, the bubbles remaining at the interface between the object to be bonded and the adhesive layer quickly disappear, A transparent surface material with an adhesive layer in which no defects remain can be produced. This transparent surface material with an adhesive layer is useful as a protective plate for display panels, a protective plate for coordinate input devices, a substrate with transparent electrodes for coordinate input devices, and the like.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2014-085423 filed on April 17, 2014 are incorporated herein by reference. .
1 粘着層付き透明面材
2 粘着層付き透明面材
3 表示装置
10 透明面材
12 遮光印刷部
14 粘着層
15 堰
16 保護フィルム
18 第一組成物
20 部分硬化物の層
22 未硬化の堰
24 領域
26 第一組成物
28 下定盤
30 ディスペンサ
32 送りねじ
34 送りねじ
36 支持面材
38 減圧装置
40 吸着パッド
42 上定盤
44 下定盤
46 エアシリンダ
48 真空ポンプ
50 表示パネル
52 透明基板
54 透明基板
56 液晶層
58 偏光板
60 フレキシブルプリント配線板
62 ダイコータ
64 LED光源 DESCRIPTION OFSYMBOLS 1 Transparent surface material with adhesion layer 2 Transparent surface material with adhesion layer 3 Display apparatus 10 Transparent surface material 12 Light-shielding printing part 14 Adhesion layer 15 Weir 16 Protective film 18 1st composition 20 Layer of partially cured material 22 Uncured weir 24 Area 26 First composition 28 Lower surface plate 30 Dispenser 32 Feed screw 34 Feed screw 36 Support surface material 38 Pressure reducing device 40 Suction pad 42 Upper surface plate 44 Lower surface plate 46 Air cylinder 48 Vacuum pump 50 Display panel 52 Transparent substrate 54 Transparent substrate 56 Liquid crystal layer 58 Polarizing plate 60 Flexible printed wiring board 62 Die coater 64 LED light source
2 粘着層付き透明面材
3 表示装置
10 透明面材
12 遮光印刷部
14 粘着層
15 堰
16 保護フィルム
18 第一組成物
20 部分硬化物の層
22 未硬化の堰
24 領域
26 第一組成物
28 下定盤
30 ディスペンサ
32 送りねじ
34 送りねじ
36 支持面材
38 減圧装置
40 吸着パッド
42 上定盤
44 下定盤
46 エアシリンダ
48 真空ポンプ
50 表示パネル
52 透明基板
54 透明基板
56 液晶層
58 偏光板
60 フレキシブルプリント配線板
62 ダイコータ
64 LED光源 DESCRIPTION OF
Claims (18)
- 透明面材と、前記透明面材の少なくとも一方の表面に形成された、硬化性樹脂組成物の硬化物からなる粘着層とを有し、
前記粘着層中の水酸基の濃度が、100×10-6~600×10-6モル/gであり、
前記粘着層中のウレタン結合の濃度が、0~150×10-6モル/gである、粘着層付き透明面材。 A transparent surface material, and an adhesive layer made of a cured product of the curable resin composition, formed on at least one surface of the transparent surface material,
The concentration of the hydroxyl group in the adhesive layer is 100 × 10 −6 to 600 × 10 −6 mol / g,
A transparent face material with an adhesive layer, wherein the concentration of urethane bonds in the adhesive layer is 0 to 150 × 10 −6 mol / g. - 前記粘着層中の水酸基の濃度と前記粘着層中のウレタン結合の濃度との合計が、100×10-6~750×10-6mol/gである、請求項1に記載の粘着層付き透明面材。 2. The transparent with adhesive layer according to claim 1, wherein the total of the concentration of hydroxyl groups in the adhesive layer and the concentration of urethane bonds in the adhesive layer is 100 × 10 −6 to 750 × 10 −6 mol / g. Face material.
- 前記粘着層の溶解度パラメータが、17.5~18.5(J/cm3)1/2である、請求項1または2に記載の粘着層付き透明面材。 The transparent surface material with an adhesive layer according to claim 1 or 2, wherein the solubility parameter of the adhesive layer is 17.5 to 18.5 (J / cm 3 ) 1/2 .
- 前記硬化性樹脂組成物が、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)とを含み、
前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有し、
前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、ウレタン結合を有していてもよい、請求項1~3のいずれか一項に記載の粘着層付き透明面材。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond,
Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) have a hydroxyl group,
The pressure-sensitive adhesive layer according to any one of claims 1 to 3, wherein either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond. With transparent face material. - 前記硬化性樹脂組成物が、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、
前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有し、
前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、ウレタン結合を有していてもよい、請求項1~3のいずれか一項に記載の粘着層付き透明面材。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond,
At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C) has a hydroxyl group,
4. The method according to claim 1, wherein at least one of the curable oligomer (A), the low molecular weight polymerizable compound (B), and the non-curable oligomer (C) may have a urethane bond. The transparent surface material with the adhesion layer of one term | claim. - 前記粘着層の表面を覆う、剥離可能な保護フィルムをさらに有する、請求項1~5のいずれか一項に記載の粘着層付き透明面材。 The transparent surface material with an adhesive layer according to any one of claims 1 to 5, further comprising a peelable protective film covering the surface of the adhesive layer.
- 請求項1~6のいずれか一項に記載の粘着層付き透明面材を製造する方法であって、下記工程(α)および下記工程(γ)を有する、粘着層付き透明面材の製造方法。
(α)前記透明面材の表面に液状の前記硬化性樹脂組成物を供給し、必要に応じて前記硬化性樹脂組成物を部分的に硬化させて部分硬化物とする工程。
(γ)前記硬化性樹脂組成物または前記部分硬化物を硬化させて、前記粘着層を形成する工程。 A method for producing a transparent surface material with an adhesive layer according to any one of claims 1 to 6, comprising the following step (α) and the following step (γ). .
(Α) A step of supplying the liquid curable resin composition to the surface of the transparent surface material and partially curing the curable resin composition as necessary to obtain a partially cured product.
(Γ) A step of curing the curable resin composition or the partially cured product to form the adhesive layer. - 下記工程(β)をさらに有する、請求項7に記載の粘着層付き透明面材の製造方法。
(β)前記硬化性樹脂組成物または前記部分硬化物の表面を保護フィルムで覆う工程。 The manufacturing method of the transparent surface material with the adhesion layer of Claim 7 which further has the following process ((beta)).
(Β) A step of covering the surface of the curable resin composition or the partially cured product with a protective film. - 前記工程(α)が、下記工程(α1)であり、前記工程(β)が、下記工程(β1)であり、前記工程(γ)が、下記工程(γ1)である、請求項8に記載の粘着層付き透明面材の製造方法。
(α1)前記透明面材の表面に液状の前記硬化性樹脂組成物を層状に供給し、前記透明面材の表面に供給された前記硬化性樹脂組成物を部分的に硬化させて部分硬化物の層を形成する工程。
(β1)前記部分硬化物の層の表面を保護フィルムで覆う工程。
(γ1)前記部分硬化物の層をさらに硬化させて、前記粘着層を形成する工程。 The step (α) is the following step (α1), the step (β) is the following step (β1), and the step (γ) is the following step (γ1). Manufacturing method of transparent face material with adhesive layer.
(Α1) The liquid curable resin composition is supplied in a layer form on the surface of the transparent face material, and the curable resin composition supplied on the surface of the transparent face material is partially cured to be partially cured. Forming a layer.
(Β1) A step of covering the surface of the partially cured product layer with a protective film.
(Γ1) A step of further curing the partially cured product layer to form the adhesive layer. - 前記工程(α)が、下記工程(α21)および下記工程(α22)であり、前記工程(β)が、下記工程(β2)であり、前記工程(γ)が、下記工程(γ21)および下記工程(γ22)である、請求項8に記載の粘着層付き透明面材の製造方法。
(α21)前記透明面材の表面の周縁部に枠状の堰を形成する工程。
(α22)前記堰で囲まれた領域に前記硬化性樹脂組成物を供給する工程。
(β2)減圧雰囲気下にて、前記硬化性樹脂組成物の層の上に、保護フィルム付き支持面材を、前記保護フィルムが前記硬化性樹脂組成物の層の表面に接するように重ねて、前記透明面材、前記保護フィルムおよび前記堰で前記硬化性樹脂組成物の層が密封された積層体を得る工程。
(γ21)前記工程(β2)より高い圧力雰囲気下に前記積層体を置いた状態にて、前記硬化性樹脂組成物の層を硬化させて、前記粘着層を形成する工程。
(γ22)前記工程(γ21)の後、前記支持面材を前記保護フィルムから剥離する工程。 The step (α) is the following step (α21) and the following step (α22), the step (β) is the following step (β2), and the step (γ) is the following step (γ21) and the following step (γ21). The manufacturing method of the transparent surface material with the adhesion layer of Claim 8 which is a process ((gamma) 22).
(Α21) A step of forming a frame-like weir at the peripheral edge of the surface of the transparent face material.
(Α22) A step of supplying the curable resin composition to a region surrounded by the weir.
(Β2) Under a reduced-pressure atmosphere, the support surface material with a protective film is stacked on the curable resin composition layer so that the protective film is in contact with the surface of the curable resin composition layer, The process of obtaining the laminated body by which the layer of the said curable resin composition was sealed with the said transparent surface material, the said protective film, and the said dam.
(Γ21) A step of forming the adhesive layer by curing the layer of the curable resin composition in a state where the laminate is placed under a higher pressure atmosphere than in the step (β2).
(Γ22) A step of peeling the support surface material from the protective film after the step (γ21). - 表示パネルと、
前記粘着層が前記表示パネルに接するように、前記表示パネルに貼合された、請求項1~5のいずれか一項に記載の粘着層付き透明面材と、
を有する表示装置。 A display panel;
The transparent surface material with the adhesive layer according to any one of claims 1 to 5, which is bonded to the display panel so that the adhesive layer is in contact with the display panel;
A display device. - 請求項11に記載の表示装置を製造する方法であって、
減圧雰囲気下にて、前記表示パネルと前記粘着層付き透明面材とを、前記粘着層が前記表示パネルに接するように重ねて貼合する、表示装置の製造方法。 A method for manufacturing the display device according to claim 11, comprising:
The manufacturing method of the display apparatus which piles up and bonds the said display panel and the said transparent surface material with an adhesion layer so that the said adhesion layer may contact the said display panel in a pressure-reduced atmosphere. - 硬化性樹脂組成物の硬化物からなる粘着シートであり、
前記粘着シート中の水酸基の濃度が、100×10-6~600×10-6モル/gであり、
前記粘着シート中のウレタン結合の濃度が、0~150×10-6モル/gである、粘着シート。 It is an adhesive sheet made of a cured product of a curable resin composition,
The concentration of hydroxyl groups in the pressure-sensitive adhesive sheet is 100 × 10 −6 to 600 × 10 −6 mol / g,
The pressure-sensitive adhesive sheet has a urethane bond concentration in the pressure-sensitive adhesive sheet of 0 to 150 × 10 −6 mol / g. - 前記粘着シート中の水酸基の濃度と前記粘着シート中のウレタン結合の濃度との合計が、100×10-6~750×10-6mol/gである、請求項13に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 13, wherein the total of the concentration of hydroxyl groups in the pressure-sensitive adhesive sheet and the concentration of urethane bonds in the pressure-sensitive adhesive sheet is 100 × 10 −6 to 750 × 10 −6 mol / g.
- 前記硬化性樹脂組成物の硬化物の溶解度パラメータが、17.5~18.5(J/cm3)1/2である、請求項13または14に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 13 or 14, wherein the solubility parameter of the cured product of the curable resin composition is 17.5 to 18.5 (J / cm 3 ) 1/2 .
- 前記硬化性樹脂組成物が、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)とを含み、
前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、水酸基を有し、
前記硬化性オリゴマー(A)および前記低分子量重合性化合物(B)のいずれか一方または両方が、ウレタン結合を有していてもよい、請求項13~15のいずれか一項に記載の粘着シート。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, and a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond,
Either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) have a hydroxyl group,
The pressure-sensitive adhesive sheet according to any one of claims 13 to 15, wherein either one or both of the curable oligomer (A) and the low molecular weight polymerizable compound (B) may have a urethane bond. . - 前記硬化性樹脂組成物が、付加重合性不飽和二重結合を有する硬化性オリゴマー(A)と、付加重合性不飽和二重結合を有する低分子量重合性化合物(B)と、付加重合性不飽和二重結合を有しない非硬化性オリゴマー(C)とを含み、
前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、水酸基を有し、
前記硬化性オリゴマー(A)、前記低分子量重合性化合物(B)および前記非硬化性オリゴマー(C)のうち少なくとも1つが、ウレタン結合を有していてもよい、請求項13~15のいずれか一項に記載の粘着シート。 The curable resin composition comprises a curable oligomer (A) having an addition polymerizable unsaturated double bond, a low molecular weight polymerizable compound (B) having an addition polymerizable unsaturated double bond, and an addition polymerizable non-polymerizable compound. A non-curable oligomer (C) having no saturated double bond,
At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C) has a hydroxyl group,
At least one of the curable oligomer (A), the low molecular weight polymerizable compound (B) and the non-curable oligomer (C) may have a urethane bond. The pressure-sensitive adhesive sheet according to one item. - 請求項13~17のいずれか一項に記載の粘着シートと、
前記粘着シートの少なくとも一方の表面を覆う、剥離可能な保護フィルムと、
を有する、保護フィルム付き粘着シート。 The pressure-sensitive adhesive sheet according to any one of claims 13 to 17,
A peelable protective film covering at least one surface of the pressure-sensitive adhesive sheet;
A pressure-sensitive adhesive sheet with a protective film.
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